CN110339847A - Denitrating catalyst and its preparation method and application - Google Patents
Denitrating catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of denitrating catalyst and its preparation method and application.The denitrating catalyst includes the CeO for adulterating Mn compound2, wherein the molar ratio of Ce atom and Mn atom is 0.2~5:1；The average grain diameter of the denitrating catalyst is 1~100nm；The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion.Denitrating catalyst of the invention has excellent denitration efficiency, and cheap, environmental-friendly, no overt toxicity.Further, the denitrating catalyst can also remove volatile organic matter containing chlorine while removing nitrogen oxides, with excellent anti-chlorine poisoning capability, to the cooperation-removal of nitrogen oxides and the volatile organic matter containing chlorine suitable for the industries flue gases such as metallurgy, steel sintering and waste incineration.
Description
Technical field
The present invention provides a kind of denitrating catalyst and its preparation method and application, belongs to catalyst field.
Background technique
Rubbish volume reduction, decrement not only may be implemented in waste incineration, can also realize garbage as resource, energy.However, rubbish
Rubbish burns produced pollution object and seriously threatens ecological environment and human health.
The organic compound of volatile containing chlorine (CVOCs) is the hot and difficult issue of environmental catalysis area research, wherein contains chlorine
Volatile organic matter is the very strong organic compound of volatile containing chlorine of toxicity, seriously pollutes environment, has carcinogenesis to human body.
Volatile organic matter containing chlorine is the general designation for the aromatic compounds that more chlorine replace oxygen-containing tricyclic, specifically includes more chloro dibenzo-
P- volatile organic matter containing chlorine (polychlorinated dibenzo-p-dioxins, PCDDs), polychlorinated dibenzofurans
(polychlorinated dibenzofurans, PCDFs) and 2,3,7,8- tetra- chloro dibenzo-p- volatility containing chlorine is organic
Object (2,3,7,8-tetrachlorodibenzo-p-dioxin, TCDD) etc..Waste incineration, steel sintering and nonferrous smelting etc.
Industry is its main source.Nitrogen oxides is one of atmosphere pollution major pollutants, is directly detrimental to health, moreover it is possible to cause light
Chemical fumes, acid rain, depletion of the ozone layer promote the environmental problems such as the generation of secondary aerosol species.
Now, nitrogen oxides generally is removed using commercial catalysts, recycles adsorption technology to remove volatility containing chlorine organic
Object.Such as: commercial catalysts V2O5-WO3/TiO2Operating temperature window be generally 300~400 DEG C, traditional high temperature denitration
Catalyst is not suitable for waste incineration and the metallurgy industry denitrating flue gas of emission status complexity.Compared with directly thermally decomposing, catalysis
Volatile organic matter containing chlorine is degraded to harmless product CO in relatively lower temp by oxidation technology2、HCl/Cl2And H2O.In addition,
Adsorption technology can only will contain chlorine volatile organic matter and be transferred in another transfer, and there may be secondary during adsorbent reactivation
Pollution.
" consumer waste incineration contamination control standard " (GB 18485-2014) regulation: the nitrogen oxides of incinerator and contain chlorine
The discharge amount of volatile organic matter is respectively smaller than 100mg/Nm3、0.1ng TEQ/Nm3.Therefore, nitrogen oxides catalysis reduction and
The catalysis oxidation of the volatile organic matter containing chlorine requires the redox property of catalyst.
Manganese-based catalyst is a kind of excellent low temperature catalyst.But the manganese base for removing the volatile organic matter containing chlorine
After long-play fluorine poisoning often occurs for catalyst, is poisoned and loses catalytic activity, and it is big that this becomes catalytic combustion technology
The technical bottleneck of sizable application.It is increasingly strict with China's Air Pollutant Emission regulation, will have a large amount of waste incinerator,
The needs such as steel sintering furnace, non-ferrous metal smelting furnace increase or update flue gas pollutant emission control systems.
Citation [1] discloses a kind of manganese tin ce composite oxidation catalyst, the manganese tin ce composite oxidation catalyst
Preparation method include following steps: 1) to MnSO4·H2O、SnCl4·5H2O and (NH4)2S2O8Add in mixture aqueous solution
Entering mass percent concentration is 20%~30% ammonium hydroxide, is vigorously stirred at 40 DEG C~60 DEG C to pH value of solution=9~12, is sunk
Starch and mother liquor；2) by sediment in mother liquor aging, filter, be washed with distilled water to until filtrate is in neutrality, sediment exists
70 DEG C~110 DEG C dry 8h~16h, the sample after drying roasts in air obtains manganese tin ce composite oxidation catalyst.
Contain tin in the catalyst, it is expensive, and the catalyst is not suitable for the removing to nitrogen oxides.
Citation [2] is related to a kind of with low temperature photo-thermal concerted catalysis purifying VOCs and light auxiliary self-repair function
MnOx-CeO2The preparation method of composite semiconductor catalyst, the MnOx-CeO2The chemical formula of composite semiconductor catalyst is
Ce1-aMnaO2-δ, wherein 0 < a < 0.7；The described method includes: 1) weigh Ce salt and KMnO4, it is dissolved in aqueous slkali, it is outstanding obtains mixing
Supernatant liquid；2) mixing suspension is sealed and carries out hydro-thermal reaction, obtain sediment；3) sediment of preparation, washing, drying are isolated
Grinding obtains the MnO afterwardsx-CeO2Composite semiconductor catalyst.The catalyst is living suitable for the catalysis of catalysis oxidation VOCs
Property, it is not suitable for removing volatile organic matter containing chlorine.
Therefore, in conjunction with the exhaust temperature of the industries flue gas such as waste incineration, metallurgy, rationally designing bifunctional catalyst will be realized
The synergistic purification of two kinds of pollutants, and the discharge of nitrogen oxides and the volatile organic matter containing chlorine is controlled for improving urban environment tool
It is of great significance.
Citation:
Citation [1]: CN109092325A
Citation [2]: CN104338529A
Summary of the invention
Problems to be solved by the invention
In view of the technical problems existing in the prior art, one of the objects of the present invention is to provide a kind of denitrating catalyst,
The denitrating catalyst has low-temperature denitration ability in preferable, and can also remove while removing nitrogen oxides and volatilize containing chlorine
Property organic matter, have excellent anti-chlorine poisoning capability.
Further, the present invention also provides a kind of preparation method of denitrating catalyst, the raw material of the preparation method is easy to
It obtains, technical process is simply nontoxic.
Further, the denitrating catalyst is suitable for the industries flue gases such as metallurgy, steel sintering and waste incineration to nitrogen oxygen
The cooperation-removal of compound and the volatile organic matter containing chlorine.
The solution to the problem
[1], a kind of denitrating catalyst comprising the CeO of doping Mn compound2, wherein
The molar ratio of Ce atom and Mn atom is 0.2~5:1；
The average grain diameter of the denitrating catalyst is 1~100nm；
The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion.
[2], the denitrating catalyst according to [1], wherein the inorganic acid radical ion includes halide ion, PO4 3-、
SO4 2-、H2PO4 -、NO3 -One or more of combination.
[3], the denitrating catalyst according to [1] or [2], wherein the denitrating catalyst indicates are as follows:
A-MnCe
Wherein, A is from the active ion in living solution, and the living solution is including at least a kind of active ion
Acid solution and/or salting liquid；The salting liquid is preferably ammonium salt solution；
Preferably, the acid solution includes H3PO4、HF、HCl、HBr、HI、H2SO4And HNO3One or more of
Combination；The ammonium salt solution includes NH4F、NH4Cl、NH4Br、NH4I、NH4NO3、(NH4)2SO4、NH4H2PO4One of or
Two or more combinations.
[4], according to [1]-[3] described in any item denitrating catalysts, wherein the specific surface area of the denitrating catalyst is
10~300m2/g。
[5], a kind of preparation method of denitrating catalyst, wherein after the preparation method is prepared including the use of coprecipitation
The step of being modified processing；Wherein, the denitrating catalyst includes:
The molar ratio of Ce atom and Mn atom is 0.2~5:1；
The average grain diameter of the denitrating catalyst is 1~100nm；
The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion.
[6], the preparation method according to [5], wherein
It takes manganese presoma and cerium precursor to dissolve and mixes, obtain precursor solution；
Precursor solution is placed in aging in aqueous slkali, generates crystal grain；
The crystal grain is roasted, product of roasting is obtained；
The product of roasting is placed in living solution and is modified processing, obtains denitrating catalyst；Wherein,
The living solution is the acid solution and/or salting liquid including at least a kind of active ion；The salting liquid is preferred
For ammonium salt solution.
[7], the preparation method according to [6], wherein the manganese presoma include manganese nitrate, manganese sulfate, manganese chloride and
The combination of one or more of manganese acetate；
The cerium precursor includes the combination of one or more of cerium chloride, cerous sulfate, cerous nitrate and cerous acetate；
The aqueous slkali is ammonia spirit, it is preferable that the ammonia spirit is the ammonium hydroxide and water that concentration is 25%~28%
Mixture, wherein the volume ratio of ammonium hydroxide and water that concentration is 25%~28% is 3:1~1:3.
[8], the preparation method according to [6] or [7], wherein ammonium hydroxide used in every generation 1mol denitrating catalyst
The content of ammonium ion is 10~15mol in solution；
The time of the aging is 1~10h；
The time of the roasting is 2~6h, and the temperature of the roasting is 400~650 DEG C；
The concentration of the living solution is 0.01~1mol/L, and the time of the modification is 10~60min.
[9], according to [6]-[8] described in any item preparation methods, wherein the acid solution includes H3PO4、HF、HI、
HCl、HBr、H2SO4And HNO3One or more of combination；
The ammonium salt solution includes NH4F、NH4Cl、NH4Br、NH4I、NH4NO3、(NH4)2SO4、NH4H2PO4One of or
Two or more combinations.
[10], a kind of basis [1]-[4] described in any item denitrating catalysts or [5]-[9] described in any item preparations
The purposes of the denitrating catalyst that method is prepared Catalytic Decomposition of Nitric Oxide and the volatile organic matter containing chlorine in flue gas.
The effect of invention
Denitrating catalyst of the invention has excellent denitration efficiency, and cheap, environmental-friendly, no overt toxicity.
Further, which can also remove volatile organic matter containing chlorine while removing nitrogen oxides, tool
There is excellent anti-chlorine poisoning capability, to nitrogen oxides and contains suitable for the industries flue gas such as metallurgy, steel sintering and waste incineration
The cooperation-removal of chlorine volatile organic matter.
Further, the raw material of the preparation method of denitrating catalyst of the invention, the preparation method is easily obtained, technique mistake
Journey is easy to operate and nontoxic, and cost is relatively low, is suitble to produce in enormous quantities.
Detailed description of the invention
Fig. 1 shows the electron microscope (scale 50nm) of denitrating catalyst of the invention；
Fig. 2 shows the electron microscopes (scale 5nm) of denitrating catalyst of the invention；
Fig. 3 show the denitrating catalyst of 1-4 of the embodiment of the present invention and comparative example 1 to removal of nitrogen oxide efficiency with
The relational graph of reaction temperature.
Fig. 4 shows 1-4 of the embodiment of the present invention and the denitrating catalyst of comparative example 1 removes volatile organic matter containing chlorine
The relational graph of efficiency and reaction temperature.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and aspect of the invention.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In other example,
Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight master of the invention
Purport.
Such as without Special Statement, unit used in the present invention is SI units, and the number occurred in the present invention
Value, numberical range should all be interpreted as containing permitted error in industrial production.
" water " used herein includes tap water, deionized water, distilled water, distilled water, pure water, ion exchange water
Etc. any feasible water.
It is indicated herein if any " about ", " basic ", " substantially " used etc., then its error range can be 5%.
" room temperature " referred to herein, temperature can be " 15~30 DEG C ".
First embodiment
First embodiment of the invention provides a kind of denitrating catalyst, and the denitrating catalyst includes doping Mn chemical combination
The CeO of object2, wherein
The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion, it is preferable that
The electronegativity of all elements of the inorganic acid radical ion can be greater than 2, such as 2.1 or more.
Further, the electronegativity of other all elements in addition to protium of the inorganic acid radical ion preferably can be big
In 2.1, more preferable electronegativity is 2.2 or more, and further preferred electronegativity is 2.3 or more, and still more preferably electronegativity is 2.4
More than, still further preferably electronegativity is 2.5 or more, and still more preferably electronegativity is 2.6 or more.Although the endless all clear of mechanism
Chu, but the electronegativity of all elements of the other all elements of inorganic acid radical ion of the invention in addition to protium is 2.6
It is more excellent to the removal efficiency of the volatile organic matter containing chlorine when above.
The anion that generates when " acid ion " as described herein is meant that acid ionization may include anaerobic acid group from
Sub and aerobic acid ion.
In the present invention, in the active ion in the surface of denitrating catalyst, so as to so that denitration catalyst of the invention
Agent is in removing nitrogen oxides (NOx) while, it can further preferably remove volatile organic matter containing chlorine.
Specifically, the inorganic acid radical ion includes halide ion, PO4 3-、SO4 2-、H2PO4 -、NO3 -Deng one of or two
Kind or more combination.Wherein, halide ion F-、Cl-、Br-、I-。
Wherein, in above-mentioned inorganic acid radical ion, the electronegativity of protium is 2.1, and the electronegativity of nitrogen is 3.04, oxygen member
The electronegativity of element is 3.44, and the electronegativity of fluorine element is 4.0, and the electronegativity of P elements is 2.19, and the electronegativity of element sulphur is
2.58, the electronegativity of chlorine element is 3.16, and the electronegativity of bromo element is 2.96, and the electronegativity of iodine is 2.66.
Specifically, in the present invention, in order to play the effect of denitrating catalyst preferably, Ce atom rubs with Mn atom
You are than being 0.5~5:1；Preferably 1~4:1, more preferable 1~3:1, further preferred 1~2:1, still more preferably 1.2~
1.8:1.For example: the molar ratio of Ce atom and Mn atom can be 0.8:1, can be 1:1,1.2:1,1.8:1,2:1,
2.5:1 waiting.
In general, the average grain diameter of the denitrating catalyst of the invention is 1~100nm, preferably 1.5~80nm, more preferable 2
~60nm, further preferred 2.5~40nm, such as: 3~20nm, 3-10nm etc..
Figures 1 and 2 show that the electron microscope of denitrating catalyst of the invention, wherein Fig. 1 is measured when scale is 50nm
, Fig. 2 is measured when scale is 5nm.Denitrating catalyst of the invention exists in pelletized form it can be seen from Fig. 1 and Fig. 2.
In addition, the rough lattice structure of denitrating catalyst of the invention as seen from Figure 2.
In the present invention, Mn compound can be Mn oxide, such as: MnO2, Mn2O3, Mn3O4One or both of Deng
Above combination.
Specifically, denitrating catalyst of the invention can indicate are as follows:
A-MnCe
Wherein, A is from the active ion in living solution, and the living solution is including at least a kind of active ion
Acid solution and/or salting liquid.By using acid solution and/or salting liquid, so that the surface of denitrating catalyst of the invention has
Active ion.Preferably, the salting liquid is ammonium salt solution.
Specifically, the present invention is not particularly limited the composition of living solution, and can be this field usually can make denitration
The surface of catalyst generates the solution of active ion.For example, the acid solution includes H3PO4、HF、HI、HBr、HCl、
H2SO4And HNO3Deng one or more of combination；The salting liquid includes NH4F、NH4Cl、NH4Br、NH4I、
NH4NO3、(NH4)2SO4、NH4H2PO4Deng one or more of combination.
Preferably, the specific surface area of the denitrating catalyst is 10~300m2/ g, preferably 20~250m2/ g, more preferably
For 30~200m2/ g, further preferably 40~180m2/ g is still more preferably 50~150m2/ g, such as: 85~
110m2/g。
Further, in denitrating catalyst of the invention preferably without containing denitrating catalyst of the invention concrete composition with
Outer other carrier components.Such as the substance without containing molecular sieve etc. as carrier.Denitrating catalyst of the invention is not containing
Activity when other carrier components is stronger.
Denitrating catalyst of the invention has excellent middle low-temperature denitration ability, and cheap, environmental-friendly, without obvious
Toxicity.Also, the denitrating catalyst can also remove volatile organic matter containing chlorine while removing nitrogen oxides, have excellent
Anti-chlorine poisoning capability.
The main reason for flue gas is the mixture of gas and flue dust, is pollution atmosphere.The comparison of ingredients of flue gas is complicated, although
It is defined in the world it is different in every country or international organization, but include in usually such gas water vapour,
SO2、N2、O2、CO、CO2, hydrocarbon and oxynitrides etc..But for metallurgy, steel sintering and waste incineration etc.
Industry also contains volatile organic matter containing chlorine in flue gas other than containing above-mentioned gas.And denitrating catalyst of the invention is special
Not Shi Yongyu under middle low temperature condition in flue gas Catalytic Decomposition of Nitric Oxide and volatile organic matter containing chlorine simultaneously.Especially suitable for
To the cooperation-removal of nitrogen oxides and the volatile organic matter containing chlorine in the flue gases of industries such as metallurgy, steel sintering and waste incineration.
Specifically, in the present invention, the middle low temperature can be 650 DEG C hereinafter, it is preferred that can be 600 DEG C hereinafter, can be with
Be 500 DEG C hereinafter, can be 400 DEG C hereinafter, can be 300 DEG C it is such as the following.
<second embodiment>
In second embodiment of the present invention, a kind of preparation method of the denitrating catalyst of first embodiment is provided,
The step of preparation method carries out modification after preparing including the use of coprecipitation.
<coprecipitation>
Coprecipitation refers to that they are added in the solution containing two or more cations homogeneously to exist in solution
The uniform precipitating of various composition can be obtained after precipitation reaction in precipitating reagent, is prepared containing two or more metal member
The important method of the Ultrafines for complex oxide body of element.
The present invention uses coprecipitation, can directly obtain powder body material by carrying out chemical reaction in the solution.Specifically,
During co-precipitation, the process conditions that can control include: the kind of stoicheiometry, solution concentration, solution temperature, dispersing agent
Class and quantity, hybrid mode, stirring rate, pH value, mode of washing, drying temperature and mode, maturing temperature and mode etc..Pass through
Above-mentioned process conditions are controlled, to obtain that chemical component is uniform, the small powder body material being evenly distributed of granularity.
Specifically, the average grain diameter for the denitrating catalyst that the present invention is obtained by coprecipitation is 1~100nm.
In preparation-obtained denitrating catalyst, the molar ratio of Ce atom and Mn atom is 0.2~5:1；Preferably 1~
4:1, more preferable 1~3:1, further preferred 1~2:1, still more preferably 1.2~1.8:1.For example: Ce atom and Mn
The molar ratio of atom can be 0.8:1, can be 1:1,1.2:1,1.8:1,2:1,2.5:1 etc..
By modification, the active ion in the surface of the denitrating catalyst can be made, the active ion includes
The electronegativity of inorganic acid radical ion, all elements of the inorganic acid radical ion can be greater than 2.So that denitration of the invention
Catalyst can also remove volatile organic matter containing chlorine while nitrogen oxides is desorbed.
Specifically, preparation method of the invention the following steps are included:
It takes manganese presoma and cerium precursor to dissolve and mixes, obtain precursor solution；
Precursor solution is placed in aging in aqueous slkali, generates crystal grain；
The crystal grain is roasted, product of roasting is obtained；
The product of roasting is placed in living solution and is modified processing, obtains denitrating catalyst；Wherein,
The living solution is the acid solution and/or salting liquid including at least a kind of active ion；The salting liquid is preferred
For ammonium salt solution.
<precursor solution>
It include manganese presoma and cerium precursor, i.e. manganese presoma and cerium precursor in precursor solution in the present invention
Mixed solution.Specifically, water can be used and prepare precursor solution.For example: manganese presoma and cerium precursor can be weighed
Body is dissolved in the water, and stirs to being completely dissolved, obtains precursor solution.
Specifically, the manganese presoma can be water-soluble salt containing manganese, such as: the manganese presoma may include
The combination of one or more of manganese nitrate, manganese sulfate, manganese chloride and manganese acetate.The cerium precursor can be containing cerium
Water-soluble salt, such as: the cerium precursor may include one kind or two of cerium chloride, cerous sulfate, cerous nitrate and cerous acetate
Kind or more combination.
<aging>
Precursor solution is placed in aging in aqueous slkali by the present invention, to generate crystal grain.It specifically can be by precursor solution
It is immediately placed in aqueous slkali, stirs aging at room temperature, so that grained precipitation, growth.Preferably, the time of the aging be 1~
10h。
In the ageing process, for the other conditions of aging process, also there is no particular limitation, such as can be in air
Under the conditions of carry out etc..
<aqueous slkali>
Aqueous slkali of the invention can be can generate all feasible aqueous slkalis of crystal grain, such as urea, NaOH,
The alkaline solutions such as KOH.
Specifically, it is preferable to use ammonia spirits for aqueous slkali of the invention, have precipitating rapidly as precipitating reagent, residue
The advantages that few.Preferably, the ammonia spirit is the mixture of ammonium hydroxide and water that concentration is 25%~28%, wherein concentration is
25%~28% ammonium hydroxide and the volume ratio of water are 3:1~1:3.Such as: the volume ratio of ammonium hydroxide and water is 2.5:1,2:1,1.5:
1,1:1,1:1.5,1:2,1:2.5.
When being prepared, every content for generating ammonium ion in ammonia spirit used in 1mol denitrating catalyst is 10
~15mol, such as: in used ammonia spirit the content of ammonium ion can for 10mol, 11mol, 12mol, 13mol,
14mol etc..
<standing, washing, drying>
It can also usually include the steps that standing, washing and/or drying before the firing.
Specifically, carrying out standing can make crystal grain continue agglomeration, it is however generally that, the time of standing can be 1~5h.
After being washed, can first it be dried again after being separated by solid-liquid separation, the separation of solid and liquid can be filtering, from
Heart processing etc..In general, the number of the number and separation of solid and liquid that are washed is identical.Such as: carry out washing and solid-liquid
Isolated number can be 3~5 times.
In the present invention, the temperature of the drying can be 100~120 DEG C, and the time of the drying is 4~10h.
The concentration of the living solution is 0.01~1mol/L, and the time of modification is 10~60min.
<roasting>
The present invention is by the crystal grain roasting to generation, to obtain product of roasting.Specifically, the time of the roasting
For 4~10h, the temperature of the roasting is 400~650 DEG C.
It for the device of roasting, is not particularly limited, tube furnace, Muffle furnace etc. can be used for example.
Other conditions of roasting are also not particularly limited in the present invention, such as: it can be in vacuum state, inert gas shielding
Or carried out under air conditions, the inert gas can be nitrogen etc..It is preferred that can directly be carried out under air conditions.
<modification>
The product of roasting is placed in living solution and is modified processing by the present invention, to obtain denitrating catalyst.It is logical
Cross modification, can make the active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical from
The electronegativity of son, all elements of the inorganic acid radical ion can be greater than 2.The inorganic acid radical ion is first embodiment
In inorganic acid radical ion.
Specifically, the living solution is the acid solution and/or salting liquid including at least a kind of active ion.The acid is molten
Liquid or salting liquid are acid solution or salting liquid described in first embodiment.For example, the acid solution includes H3PO4、
HF、HI、HBr、HCl、H2SO4And HNO3One or more of combination；The salting liquid includes NH4F、NH4Cl、
NH4Br、NH4I、NH4NO3、
(NH4)2SO4、NH4H2PO4Deng one or more of combination.
Preferably, the concentration of the living solution is 0.01~1mol/L, the time of modification is 10~60min.
For example, 1kg product of roasting is placed in the living solution of 10~50L, room temperature by the living solution that can prepare 0.1mol/L
Stir 10~60min.
After modified processing, it is generally obtained suspension, which is washed to neutrality, overnight in 60~120 DEG C
It is dry, obtain denitrating catalyst.
Third embodiment
Third embodiment of the present invention provide a kind of denitrating catalyst of first embodiment according to the present invention or
The denitrating catalyst that the preparation method of second embodiment of the invention is prepared Catalytic Decomposition of Nitric Oxide and contains in flue gas
The purposes of chlorine volatile organic matter.
For can be a kind of denitrating catalyst composition when removing nitrogen oxides.The denitrating catalyst combination
Object may include the various other known denitrating catalysts in this field.In the preferred embodiment of the invention, the denitration catalyst
Agent composition includes the denitrating catalyst of the present invention of at least 60 mass % or more, preferably 80 mass % or more, into one
Step is preferably 90 mass % or more, in terms of the gross mass of denitrating catalyst composition.
Denitrating catalyst of the invention can be organic with the nitrogen oxides in all flue gases of catalytic eliminating and volatile containing chlorine
Object, specifically, the flue gas may include the flue gas that the industries such as metallurgy, steel sintering and waste incineration generate.
The test method of the specific surface area of denitrating catalyst of the present invention is as follows:
Specific surface area test is carried out to denitrating catalyst using physical adsorption appearance (Mai Qike Baeyer, Japan).Specific surface area
It is calculated by Brunauer-Emmett-Teller (BET) method.Average grain diameter is obtained by XRD grain size analysis.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
H3PO4The preparation of-MnCe catalyst:
Step 1: according to the atomic molar of Mn/ (Mn+Ce) than 0.4 (Ce:Mn=1.5:1), manganese acetate 2.76g, nitre are weighed
Sour cerium 10.43g；
Step 2: the weighed manganese acetate of step 1 and cerous nitrate are dissolved in 100mL deionized water, and have been evenly stirred until
Fully dissolved；
Step 3: measuring 80mL concentrated ammonia liquor, and concentration is 25%~28%, and the dilution stirring of 80mL deionized water is added, so
After be added into step 2 acquired solution, at room temperature stir aging 2h；
Step 4: after stopping stirring, 2h is stood, precipitated product crystal grain is made to continue agglomeration；
Step 5: step 4 obtained material is centrifuged with deionized water, is washed 3 times；
Step 6: filter cake obtained by step 5 is placed in 110 ± 10 DEG C of dry 8h, the lower 600 DEG C of roastings 6h of air atmosphere is obtained
Product of roasting；
Step 7: the H of 0.1mol/L is prepared3PO4Solution takes 2g product of roasting obtained by step 6 as the H of 30mL3PO4It is molten
In liquid, 30min is stirred at room temperature；
Step 8: by the suspension filtration washing of step 7 to neutrality, 80 DEG C are dried overnight, and obtain denitrating catalyst I, note
Make H3PO4-MnCe。
Embodiment 2
NH4The preparation of F-MnCe catalyst:
Step 1: according to Mn/ (Mn+Ce) atomic molar than 0.4 (Ce:Mn=1.5:1), the manganese nitrate of 50% concentration is weighed
Solution 5.73g, cerous nitrate 10.42g；
Step 2: the weighed manganese nitrate of step 1 and cerous nitrate are dissolved in 80mL deionized water, and have been evenly stirred until
Fully dissolved；
Step 3: measuring 80mL concentrated ammonia liquor, and concentration is 25%~28%, and the dilution stirring of 80mL deionized water is added, so
After be added into step 2 acquired solution, at room temperature stir aging 2h；
Step 4: after stopping stirring, 2h is stood, precipitated product crystal grain is made to continue agglomeration；
Step 5: step 4 obtained material is centrifuged with deionized water, is washed 3 times；
Step 6: filter cake obtained by step 5 is placed in 110 ± 10 DEG C of dry 8h, the lower 600 DEG C of roastings 6h of air atmosphere is obtained
Product of roasting；
Step 7: the NH of 0.1mol/L is prepared4F solution takes the obtained 2g product of roasting of step 6 as the NH of 30mL4F
In solution, 60min is stirred at room temperature；
Step 8: by the suspension filtration washing of step 7 to neutrality, 100 DEG C are dried overnight, and obtain denitrating catalyst II,
It is denoted as NH4F-MnCe。
In embodiment 2, the specific surface area of denitrating catalyst II is 94m2/ g, average grain diameter 5nm.
Embodiment 3
HNO3- MnCe catalyst
Step 1: according to Mn/ (Mn+Ce) atomic molar than 0.4 (Ce:Mn=1.5:1), the manganese nitrate of 50% concentration is weighed
Solution 5.73g, cerous acetate 8.26g；
Step 2: the weighed manganese nitrate of step 1 and cerous acetate are dissolved in 80mL deionized water, and have been evenly stirred until
Fully dissolved；
Step 3: measuring 90mL concentrated ammonia liquor, and concentration is 25%~28%, and the dilution stirring of 90mL deionized water is added, so
After be added into step 2 acquired solution, at room temperature stir aging 2h；
Step 4: after stopping stirring, 2h is stood, precipitated product crystal grain is made to continue agglomeration；
Step 5: step 4 obtained material is centrifuged with deionized water, is washed 3 times；
Step 6: filter cake obtained by step 5 is placed in 110 ± 10 DEG C of dry 8h, the lower 600 DEG C of roastings 6h of air atmosphere is obtained
Product of roasting；
Step 7: the HNO of 0.1mol/L is prepared3Solution takes the product of roasting of the obtained 2g of step 6 as 30mL's
H2SO4In solution, 40min is stirred at room temperature；
Step 8: by the suspension filtration washing of step 7 to neutrality, 110 DEG C are dried overnight, and obtain denitrating catalyst
III is denoted as HNO3-MnCe。
Embodiment 4
HCl-MnCe catalyst
Step 1: according to Mn/ (Mn+Ce) atomic molar than 0.4 (Ce:Mn=1.5:1), the manganese nitrate of 50% concentration is weighed
Solution 5.73g, cerous nitrate 10.42g；
Step 2: the weighed manganese nitrate of step 1 and cerous nitrate are dissolved in 80mL deionized water, and have been evenly stirred until
Fully dissolved；
Step 3: measuring 80mL concentrated ammonia liquor, and concentration is 25%~28%, and the dilution stirring of 80mL deionized water is added, so
After be added into step 2 acquired solution, at room temperature stir aging 3h；
Step 4: after stopping stirring, 3h is stood, precipitated product crystal grain is made to continue agglomeration；
Step 5: step 4 obtained material is centrifuged with deionized water, is washed 5 times；
Step 6: filter cake obtained by step 5 is placed in 110 DEG C of dry 10h, the lower 600 DEG C of roastings 6h of air atmosphere is roasted
Burn product；
Step 7: preparing the HCl solution of 0.1mol/L, takes the obtained 2g product of roasting of step 6 as the H of 30mL2SO4
In solution, 40min is stirred at room temperature；
Step 8: by the suspension filtration washing of step 7 to neutrality, 110 DEG C are dried overnight, and obtain denitrating catalyst IV,
It is denoted as HCl-MnCe.
Comparative example 1
Fresh-MnCe
Step 1: according to Mn/ (Mn+Ce) atomic molar than 0.4 (Ce:Mn=1.5:1), the manganese nitrate of 50% concentration is weighed
Solution 5.73g, cerous nitrate 10.42g；
Step 2: the weighed manganese nitrate of step 1 and cerous nitrate are dissolved in 80mL deionized water, and have been evenly stirred until
Fully dissolved；
Step 3: measuring 80mL concentrated ammonia liquor, and concentration is 25%~28%, and the dilution stirring of 80mL deionized water is added, so
After be added into step 2 acquired solution, at room temperature stir aging 3h；
Step 4: after stopping stirring, 3h is stood, precipitated product crystal grain is made to continue agglomeration；
Step 5: step 4 obtained material is centrifuged with deionized water, is washed 5 times；
Step 6: filter cake obtained by step 5 is placed in 110 DEG C of dry 10h, the lower 600 DEG C of roastings 6h of air atmosphere obtains 10g
Fresh catalyst.
Catalyst activity test
Test condition: by denitrating catalyst pressed powder, broken, screening, the embodiment 1-4 of 40~60 mesh and right is chosen
The denitrating catalyst of ratio 1 is used for pollutant Collaborative Control activity rating, 100g catalyst, NO 500ppm, NH3500ppm,
C6H5Cl (analogies of volatile organic matter containing chlorine) 50ppm, O210vol.%, N2Balance, flue gas total flow are 100mL/min,
Gas space velocity GHSV 60,000h-1(mark condition), 300 DEG C of reaction temperature；Specific test result is as shown in Figure 3-4.
Fig. 3 show the denitrating catalyst of 1-4 of the embodiment of the present invention and comparative example 1 to removal of nitrogen oxide efficiency with
The relational graph of reaction temperature.Fig. 4 shows 1-4 of the embodiment of the present invention and the denitrating catalyst of comparative example 1 volatilizees to containing chlorine
The relational graph of property organic matter removal efficiency and reaction temperature.
From test result as can be seen that with the extension of reaction time, by H3PO4The catalyst H of processing3PO4- MnCe,
Its removal of nitrogen oxide efficiency can be stablized 96%, and the removal efficiency of volatile organic matter containing chlorine can maintain 23%.With it is new
Fresh catalyst is compared, H3PO4The catalyst confrontation fluorine poisoning performance influence of processing is unobvious, but has one to removal of nitrogen oxide rate
It is fixed to improve.
With the extension of reaction time, by NH4The catalyst n H of F processing4F-MnCe, removal of nitrogen oxide efficiency are
91%, the removal efficiency of volatile organic matter containing chlorine can maintain 37%.Compared with fresh catalyst, NH4F processing can be improved
The anti-chlorine poisoning performance of catalyst.
With the extension of reaction time, by HNO3The catalyst HNO of processing3- MnCe, removal of nitrogen oxide efficiency is about
It is 90%, the removal efficiency of volatile organic matter containing chlorine can maintain 45%.Compared with fresh catalyst, HNO3Processing obviously mentions
The high anti-chlorine poisoning performance of catalyst.
With the extension of reaction time, the catalyst HCl-MnCe handled by HCl, removal of nitrogen oxide efficiency are about
92%, the removal efficiency of volatile organic matter containing chlorine can maintain 43%.Compared with fresh catalyst, HCl processing is significantly improved
The anti-chlorine poisoning performance of catalyst.In conclusion the type of processing solution is to nitrogen oxides and the volatile organic matter containing chlorine
Removal efficiency is affected, wherein uses HNO3、HCl、NH4F processing catalyst denitration efficiency and except volatility containing chlorine it is organic
The equal highest of object efficiency.Therefore, catalyst prepared by the present invention can it is preferable in low temperature remove nitrogen oxides simultaneously and waved containing chlorine
Hair property organic matter, and there is excellent anti-chlorine poisoning capability, it is a kind of environmentally friendly de- with practical application potentiality
Denox catalyst.
Industrial availability
Denitrating catalyst of the invention can industrially be produced and be catalyzed in flue gas as denitrating catalyst de-
Denitrification and apply.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of denitrating catalyst, which is characterized in that the CeO including adulterating Mn compound2, wherein
The molar ratio of Ce atom and Mn atom is 0.2~5:1；
The average grain diameter of the denitrating catalyst is 1~100nm；
The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion.
2. denitrating catalyst according to claim 1, which is characterized in that the inorganic acid radical ion include halide ion,
PO4 3-、SO4 2-、H2PO4 -、NO3 -One or more of combination.
3. denitrating catalyst according to claim 1 or 2, which is characterized in that the denitrating catalyst indicates are as follows:
A-MnCe
Wherein, A is from the active ion in living solution, and the living solution is including at least a kind of active ion
Acid solution and/or salting liquid；The salting liquid is preferably ammonium salt solution；
Preferably, the acid solution includes H3PO4、HF、HCl、HBr、HI、H2SO4And HNO3One or more of group
It closes；The ammonium salt solution includes NH4F、NH4Cl、NH4Br、NH4I、NH4NO3、(NH4)2SO4、NH4H2PO4One or both of
Above combination.
4. denitrating catalyst according to claim 1-3, which is characterized in that the specific surface of the denitrating catalyst
Product is 10~300m2/g。
5. a kind of preparation method of denitrating catalyst, which is characterized in that after the preparation method is prepared including the use of coprecipitation
The step of being modified processing；Wherein, the denitrating catalyst includes:
The molar ratio of Ce atom and Mn atom is 0.2~5:1；
The average grain diameter of the denitrating catalyst is 1~100nm；
The active ion in the surface of the denitrating catalyst, the active ion include inorganic acid radical ion.
6. preparation method according to claim 5, which is characterized in that
It takes manganese presoma and cerium precursor to dissolve and mixes, obtain precursor solution；
Precursor solution is placed in aging in aqueous slkali, generates crystal grain；
The crystal grain is roasted, product of roasting is obtained；
The product of roasting is placed in living solution and is modified processing, obtains denitrating catalyst；Wherein,
The living solution is the acid solution and/or salting liquid including at least a kind of active ion；The salting liquid is preferably ammonium
Salting liquid.
7. preparation method according to claim 6, which is characterized in that the manganese presoma includes manganese nitrate, manganese sulfate, chlorine
Change the combination of one or more of manganese and manganese acetate；
The cerium precursor includes the combination of one or more of cerium chloride, cerous sulfate, cerous nitrate and cerous acetate；
The aqueous slkali is ammonia spirit, it is preferable that the ammonia spirit is the mixed of the ammonium hydroxide that concentration is 25%~28% and water
Close object, wherein the volume ratio of ammonium hydroxide and water that concentration is 25%~28% is 3:1~1:3.
8. preparation method according to claim 6 or 7, which is characterized in that
Every content for generating ammonium ion in ammonia spirit used in 1mol denitrating catalyst is 10~15mol；
The time of the aging is 1~10h；
The time of the roasting is 2~6h, and the temperature of the roasting is 400~650 DEG C；
The concentration of the living solution is 0.01~1mol/L, and the time of the modification is 10~60min.
9. according to the described in any item preparation methods of claim 6-8, which is characterized in that the acid solution includes H3PO4、HF、
HI、HCl、HBr、H2SO4And HNO3One or more of combination；
The ammonium salt solution includes NH4F、NH4Cl、NH4Br、NH4I、NH4NO3、(NH4)2SO4、NH4H2PO4One or both of
Above combination.
10. a kind of denitrating catalyst according to claim 1-4 or the described in any item systems of claim 5-9
The purposes of the denitrating catalyst that Preparation Method is prepared Catalytic Decomposition of Nitric Oxide and the volatile organic matter containing chlorine in flue gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482192A (en) * | 2020-03-26 | 2020-08-04 | 北京碧水源科技股份有限公司 | MnO (MnO)2-Co2O3-CeO2-SnO2Deammoniation catalyst, preparation method and application |
| CN113457670A (en) * | 2021-07-16 | 2021-10-01 | 上海应用技术大学 | Low-temperature denitration catalyst resistant to halogen element Cl poisoning and preparation method and application thereof |
| CN115532273A (en) * | 2022-10-17 | 2022-12-30 | 清华大学 | Catalyst, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254464A (en) * | 2008-03-06 | 2008-09-03 | 南京工业大学 | Composite catalyst flue gas denitrating under low-temperature condition and method of preparing the same |
| CN105214652A (en) * | 2015-11-13 | 2016-01-06 | 中国科学院重庆绿色智能技术研究院 | Efficient Ce 1-xmn xo 2-δthe preparation method of solid solution low-temperature denitration catalyst and application |
| JP2017064627A (en) * | 2015-09-30 | 2017-04-06 | 日揮触媒化成株式会社 | Catalyst for exhaust gas treatment and method of producing the same |
| CN108295840A (en) * | 2018-01-24 | 2018-07-20 | 清华大学 | Manganese-based catalyst and its preparation and application of a kind of efficient synergistic purification nitrogen oxides He bioxin |
| CN109201086A (en) * | 2018-11-07 | 2019-01-15 | 清华大学盐城环境工程技术研发中心 | A kind of sulphation manganese zirconium mixed oxide catalyst and its preparation method and application |
-
2019
- 2019-08-08 CN CN201910730897.6A patent/CN110339847B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254464A (en) * | 2008-03-06 | 2008-09-03 | 南京工业大学 | Composite catalyst flue gas denitrating under low-temperature condition and method of preparing the same |
| JP2017064627A (en) * | 2015-09-30 | 2017-04-06 | 日揮触媒化成株式会社 | Catalyst for exhaust gas treatment and method of producing the same |
| CN105214652A (en) * | 2015-11-13 | 2016-01-06 | 中国科学院重庆绿色智能技术研究院 | Efficient Ce 1-xmn xo 2-δthe preparation method of solid solution low-temperature denitration catalyst and application |
| CN108295840A (en) * | 2018-01-24 | 2018-07-20 | 清华大学 | Manganese-based catalyst and its preparation and application of a kind of efficient synergistic purification nitrogen oxides He bioxin |
| CN109201086A (en) * | 2018-11-07 | 2019-01-15 | 清华大学盐城环境工程技术研发中心 | A kind of sulphation manganese zirconium mixed oxide catalyst and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111482192A (en) * | 2020-03-26 | 2020-08-04 | 北京碧水源科技股份有限公司 | MnO (MnO)2-Co2O3-CeO2-SnO2Deammoniation catalyst, preparation method and application |
| CN113457670A (en) * | 2021-07-16 | 2021-10-01 | 上海应用技术大学 | Low-temperature denitration catalyst resistant to halogen element Cl poisoning and preparation method and application thereof |
| CN115532273A (en) * | 2022-10-17 | 2022-12-30 | 清华大学 | Catalyst, preparation method and application thereof |
| CN115532273B (en) * | 2022-10-17 | 2023-12-05 | 清华大学 | Catalyst, preparation method and application thereof |
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