CN105618032A - Supported manganese based low-temperature denitration catalyst and preparation method thereof - Google Patents

Supported manganese based low-temperature denitration catalyst and preparation method thereof Download PDF

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CN105618032A
CN105618032A CN201610035584.5A CN201610035584A CN105618032A CN 105618032 A CN105618032 A CN 105618032A CN 201610035584 A CN201610035584 A CN 201610035584A CN 105618032 A CN105618032 A CN 105618032A
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salt
manganese
denitration catalyst
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CN105618032B (en
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赵春林
吴彦霞
梁海龙
唐婕
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China Building Materials Academy CBMA
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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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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

Abstract

The invention relates to a supported manganese based low-temperature denitration catalyst and a preparation method thereof. The preparation method comprises the following specific steps: (1) dissolving cerate, ferric salt or cobalt salt and manganous salt into water to form a metal salt solution, adding a nonionic surfactant, a cosurfactant and an organic solvent into the metal salt solution, and stirring till the solution is clear, thereby obtaining a microemulsion, wherein the molar ratio of the water to the nonionic surfactant to the cosurfactant to the organic solvent is equal to 1:(0.03-0.6):(0.1-1.2):(1-5); (2) adding titanium sol into the microemulsion, stirring, and regulating the pH of the microemulsion to 8-11 by a pH regulator, and heating to obtain xerogel; and (3) grinding and calcining the xerogel to obtain the denitration catalyst. According to the preparation method, active components of the catalyst are uniformly dispersed in a whole supporter, TiO2, and thus are all deposited on the supporter. The denitration catalyst has a wide temperature range of low-temperature activity and high catalytic activity.

Description

Support type manganese-based low-temperature denitration catalyst and preparation method thereof
Technical field
The present invention relates to a kind of catalyst, particularly relate to a kind of support type manganese-based low-temperature denitration catalyst and preparation method thereof.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, it is the precursor causing the problem such as acid rain, secondary fine particle. In view of NOxThe harm that ecological environment is existed, controls NOxGeneration and discharge be highly important problem. At present, NO is controlledxThe technology of discharge refers mainly to low NOxCombustion technology and flue gas NOxRemoving sulfuldioxide, and at NOxIn removing sulfuldioxide, SCR (SCR) is the gas denitrifying technology being most widely used in the world, and denitration rate can reach 90%.
At present, manganio (MnO is preparedx/TiO2) method of denitrating catalyst mainly has infusion process, coprecipitation and hydro-thermal method, these methods are it is difficult to ensure that multicomponent catalyst Homogeneous phase mixing on carrier, in the process of post processing, catalyst activity component can not be carried on carrier completely, therefore causes that the activity of catalyst can not better play a role. Prior art proposes a kind of manganese systems support type low-temperature denitration catalyst, and this catalyst is with titanyl compound for carrier, with the oxide of manganese for active component, with the oxide of tungsten for promoter, is prepared from by infusion process. The active component of this catalyst dispersibility on carrier is poor, causes that its catalysis activity is poor.
Summary of the invention
Present invention is primarily targeted at, it is provided that a kind of novel support type manganese-based low-temperature denitration catalyst and preparation method thereof, to be solved technical problem is that can carry high catalytic activity, expands low temperature active temperature range, thus more suitable for practicality.
The object of the invention to solve the technical problems realizes by the following technical solutions. Preparation method according to a kind of support type manganese-based low-temperature denitration catalyst that the present invention proposes, it is characterised in that: specifically comprise the steps of
1) by cerium salt or iron salt or cobalt salt and manganese salt formation metal salt solution soluble in water, nonionic surfactant, cosurfactant and organic solvent are joined in metal salt solution, stirs to clarify, obtain microemulsion; The molar ratio of described water, nonionic surfactant, cosurfactant and organic solvent is 1:0.03��0.6:0.1��1.2:1��5;
2) titanium colloidal sol is joined in described microemulsion, stirring, then regulating its pH value by pH adjusting agent is 8��11, heating, obtains xerogel;
3) described xerogel ground, calcine, obtain denitrating catalyst.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Preferably, the preparation method of aforesaid support type manganese-based low-temperature denitration catalyst, wherein said cerium salt or iron salt or cobalt salt and manganese salt, titanium colloidal sol consumption with the mol ratio of elemental metal for Mn:Ti:R=0.015��0.1:1:0.001��0.015, R is the one in Ce, Fe, Co element.
Preferably, the preparation method of aforesaid support type manganese-based low-temperature denitration catalyst, wherein said cerium salt is at least one in cerous nitrate, cerium chloride, cerous sulfate; Described iron salt is at least one in ferric nitrate, iron chloride, iron sulfate; Described cobalt salt is at least one in cobaltous sulfate, cobaltous chloride, cobalt nitrate; Described manganese salt is at least one in manganese sulfate, manganese acetate, manganese carbonate, manganese nitrate; Described nonionic surfactant is TritonX-100 and/or Span-80; Described cosurfactant is the one in n-butyl alcohol, hexanol, n-octyl alcohol; Described organic solvent is hexamethylene or pentane; The mass fraction of described titanium colloidal sol is 10%��30%; Step 1) described in metal salt solution in the concentration of manganese salt be 0.6��1.2mol/L, the concentration of cerium salt or iron salt or cobalt salt is 0.01��0.3mol/L.
Preferably, the preparation method of aforesaid support type manganese-based low-temperature denitration catalyst, step 2) described in pH adjusting agent be ammonia.
Preferably, the preparation method of aforesaid support type manganese-based low-temperature denitration catalyst, step 2) described in heating-up temperature be 75��100 DEG C, heat time heating time is 4-8h.
Preferably, the preparation method of aforesaid support type manganese-based low-temperature denitration catalyst, step 3) described in calcining heat be 400��700 DEG C, calcination time is 1��6h.
The object of the invention to solve the technical problems also adopts following technical scheme to realize. According to a kind of support type manganese-based low-temperature denitration catalyst that the present invention proposes, method of the present invention it is prepared from; Its active component is made up of the one in iron oxides, cerium oxide and cobalt/cobalt oxide and Mn oxide; Carrier is titanium oxide; The content of each oxide is with the mol ratio of elemental metal for Mn:Ti:R=0.015��0.1:1:0.001��0.015, and wherein, R is the one in Ce, Fe, Co element.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Preferably, aforesaid support type manganese-based low-temperature denitration catalyst, wherein said Mn oxide is MnO2��Mn2O3And Mn3O4In at least one, described titanium oxide is TiO2, described cerium oxide is CeO2And/or Ce2O3, described iron oxides is Fe3O4And/or Fe2O3, described cobalt/cobalt oxide is CoO, Co3O4And Co2O3In at least one.
Preferably, aforesaid support type manganese-based low-temperature denitration catalyst, the active component of wherein said denitrating catalyst is nano-particle, and the mean diameter of described nano-particle is 5��20nm.
Support type manganese-based low-temperature denitration catalyst prepared by the present invention carries out selective catalytic reduction reaction, and the temperature of described selective catalytic reduction reaction is 80��200 DEG C.
By technique scheme, support type manganese-based low-temperature denitration catalyst of the present invention and preparation method thereof at least has the advantage that
1. the present invention proposes a kind of reverse microemulsion system being made up of nonionic surfactant/water, define catalyst activity component nano-particle, it is possible not only to reduce the reunion of catalyst activity component nano-particle by controlling reaction condition, it is also possible to control the size of nano-particle.
2. the present invention passes through By The Microemulsion-gel Method by catalyst activity component at whole carrier TiO2In dispersed, it is achieved that catalyst activity component is all deposited on carrier, and catalyst has relatively low light-off temperature, the temperature window that higher catalysis is active and wider.
3, catalyst of the present invention has higher low-temperature denitration activity than the catalyst of the same composition prepared as carrier with titanium dioxide powder.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, and can be practiced according to the content of description, below with presently preferred embodiments of the present invention describe in detail as after.
Detailed description of the invention
For further setting forth that the present invention reaches technological means and effect that predetermined goal of the invention is taked, below in conjunction with preferred embodiment, to support type manganese-based low-temperature denitration catalyst and preparation method thereof its detailed description of the invention, feature and effect thereof of proposing according to the present invention, describe in detail as after. In the following description, what different " embodiments " or " embodiment " referred to is not necessarily same embodiment. Additionally, special characteristic or feature in one or more embodiment can be combined by any suitable form.
Embodiment 1
1) cerous nitrate of 1.79g manganese nitrate and 0.87g is dissolved in the water of 10mL being formed the mixed solution of manganese salt and cerium salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain manganese containing salt and the microemulsion of cerium salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 10, be placed in baking oven 85 DEG C heating 5h, obtain xerogel;
3) by xerogel grinding, 500 DEG C of calcining 3h, CeO is obtained2-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CeO2-MnOxNano-particle, the mean diameter of nano-particle is 11nm. The specific surface of this denitrating catalyst is 104m2/g��
Embodiment 2
1) 1.79g manganese nitrate and 0.33g iron chloride are dissolved in the water of 10mL being formed the mixed solution of manganese salt and iron salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain the microemulsion of manganese containing salt and iron salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 10, be placed in baking oven 87 DEG C heating 5h, obtain xerogel;
3) by xerogel grinding, 550 DEG C of calcining 3h, Fe is obtained2O3-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is Fe2O3-MnOxNano-particle, the mean diameter of nano-particle is 6nm. The specific surface of this denitrating catalyst is 87m2/g��
Embodiment 3
1) 1.79g manganese nitrate and 0.26 cobaltous chloride are dissolved in the water of 10mL being formed the mixed solution of manganese salt and cobalt salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain the microemulsion of manganese containing salt and cobalt salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 10, be placed in baking oven 90 DEG C heating 6h, obtain xerogel;
3) by xerogel grinding, 580 DEG C of calcining 3h, CoO-MnO is obtainedx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CoO-MnOxNano-particle, the mean diameter of nano-particle is 16nm. The specific surface of this denitrating catalyst is 63m2/g��
Embodiment 4
1) 1.39g manganese acetate and 0.44g cerous nitrate are dissolved in the water of 10mL being formed the mixed solution of manganese salt and cerium salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain manganese containing salt and the microemulsion of cerium salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 9, be placed in baking oven 85 DEG C heating 4h, obtain xerogel;
3) by xerogel grinding, 600 DEG C of calcining 3h, CeO is obtained2-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CeO2-MnOxNano-particle, the mean diameter of nano-particle is 14nm. The specific surface of this denitrating catalyst is 96m2/g��
Embodiment 5
1) 1.39g manganese acetate and 0.4g ferric sulfate solution are formed in the water of 10mL the mixed solution of manganese salt and iron salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain the microemulsion of manganese containing salt and iron salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 8, be placed in baking oven 90 DEG C heating 6h, obtain xerogel;
3) by xerogel grinding, 630 DEG C of calcining 4h, Fe is obtained2O3-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is Fe2O3-MnOxNano-particle, the mean diameter of nano-particle is 19nm. The specific surface of this denitrating catalyst is 67m2/g��
Embodiment 6
1) 1.39g manganese acetate and 0.16g cobaltous sulfate are dissolved in the water of 10mL being formed the mixed solution of manganese salt and cobalt salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain the microemulsion of manganese containing salt and cobalt salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 9, be placed in baking oven 90 DEG C heating 5h, obtain xerogel;
3) by xerogel grinding, 600 DEG C of calcining 5h, CoO-MnO is obtainedx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CoO-MnOxNano-particle, the mean diameter of nano-particle is 13nm. The specific surface of this denitrating catalyst is 51m2/g��
Embodiment 7
1) 1.79g manganese nitrate and 0.87g cerous sulfate are dissolved in the water of 10mL being formed the mixed solution of manganese salt and cerium salt, TrionX-100,17g hexanol of 71.89g and 192mL pentane are joined in above-mentioned mixed solution, stir to clarify, obtain manganese containing salt and the microemulsion of cerium salt; Wherein, the mol ratio 1:0.2:0.3:3.0 of water, TrionX-100, hexanol, pentane;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 10, be placed in baking oven 100 DEG C heating 8h, obtain xerogel;
3) by xerogel grinding, 500 DEG C of calcining 6h, CeO is obtained2-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CeO2-MnOxNano-particle, the mean diameter of nano-particle is 18nm. The specific surface of this denitrating catalyst is 72m2/g��
Embodiment 8
1) 1.79g manganese nitrate and 0.87g cerous sulfate are dissolved in the water of 10mL being formed the mixed solution of manganese salt and cerium salt, TrionX-100,7.22g n-octyl alcohol of 21.57g and 108mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain manganese containing salt and the microemulsion of cerium salt; Wherein, the mol ratio 1:0.06:0.10:1.8 of water, TrionX-100, n-octyl alcohol, hexamethylene;
2) 91.7g titanium colloidal sol (mass fraction is 18.0%) is joined in above-mentioned microemulsion, stir 1h, then regulating its pH value with ammonia is 11, be placed in baking oven 90 DEG C heating 6h, obtain xerogel;
3) by xerogel grinding, 650 DEG C of calcining 5h, CeO is obtained2-MnOx/TiO2Denitrating catalyst.
The active component of this denitrating catalyst is CeO2-MnOxNano-particle, the mean diameter of nano-particle is 20nm. The specific surface of this denitrating catalyst is 96m2/g��
Comparative example
1) cerous nitrate of 1.79g manganese nitrate and 0.87g is dissolved in the water of 10mL being formed the mixed solution of manganese salt and cerium salt, TrionX-100,8.5g hexanol of Span-80,10.75g of 7.17g and 90mL hexamethylene are joined in above-mentioned mixed solution, stir to clarify, obtain manganese containing salt and the microemulsion of cerium salt; Wherein, the mol ratio 1:0.06:0.15:1.5 of water, mixed surfactant, hexanol, hexamethylene;
2) joining in above-mentioned microemulsion by 16.5g titanium dioxide, stir 1h, then regulating its pH value with ammonia is 10, continues stirring, adds acetone, stands, sucking filtration, precipitates by a large amount of deionized waters and washing with alcohol, dries;
3) by the product of drying at 500 DEG C of roasting 3h.
The specific surface of this comparative example catalyst is 41m2/g
The catalyst that embodiment 1-8 and comparative example are prepared is for low-temperature selective catalytic reduction denitration reaction, and reaction condition and Activity Results are in Table 1.
Catalyst performance evaluation: activity experiment carries out on self-control catalyst test platform, and catalyst filling amount is 5ml, ammonia nitrogen ratio is for 1:1, O2Concentration is 6% (V/V), GHSV (per hour gas space velocity)=10000h-1Flue gas, measure the NO conversion ratio of 4 temperature spots such as 80 DEG C, 100 DEG C, 150 DEG C, 200 DEG C respectively. When temperature of reactor is stabilized to a certain temperature spot, start to pass into simulated flue gas, after reaction 10min, use flue gas analyzer (Testo350, Germany) the NO concentration in gas before and after assaying reaction, each temperature spot test constantly time is 15min, averages, NO conversion ratio, i.e. denitration rate is calculated according to formula 1.
NO conversion ratio=[(NOin-NOout)/NOin] �� 100% (formula 1)
Table 1. catalyst low-temperature selective catalytic reduction denitration reaction test Activity Results
Note: simulated flue gas forms: the NH of about NO, the 600ppm of about 600ppm3, O2Intrinsic standoff ratio 6%, all the other are balanced gas N2, air speed is 10000h-1��
Being found by the contrast of embodiment and comparative example, the specific surface of denitrating catalyst prepared by the employing sedimentation method is lower than the specific surface of the denitrating catalyst adopting By The Microemulsion-gel Method to prepare, and the denitration rate in 80��200 DEG C of temperature ranges is lower than 70%. The catalyst that titanium colloidal sol is prepared as carrier is adopted to have higher low-temperature denitration activity than the catalyst of the same composition prepared as carrier with titanium dioxide powder.
The above, it it is only presently preferred embodiments of the present invention, not the present invention is done any pro forma restriction, according to any simple modification, equivalent variations and modification that above example is made by the technical spirit of the present invention, all still falls within the scope of technical solution of the present invention.

Claims (10)

1. the preparation method of a support type manganese-based low-temperature denitration catalyst, it is characterised in that: specifically comprise the steps of
1) by cerium salt or iron salt or cobalt salt and manganese salt formation metal salt solution soluble in water, nonionic surfactant, cosurfactant and organic solvent are joined in metal salt solution, stirs to clarify, obtain microemulsion; The molar ratio of described water, nonionic surfactant, cosurfactant and organic solvent is 1:0.03��0.6:0.1��1.2:1��5;
2) titanium colloidal sol is joined in described microemulsion, stirring, then regulating its pH value by pH adjusting agent is 8��11, heating, obtains xerogel;
3) described xerogel ground, calcine, obtain denitrating catalyst.
2. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterized in that, described cerium salt or iron salt or cobalt salt and manganese salt, titanium colloidal sol consumption with the mol ratio of elemental metal for Mn:Ti:R=0.015��0.1:1:0.001��0.015, R is the one in Ce, Fe, Co element.
3. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterised in that described cerium salt is at least one in cerous nitrate, cerium chloride, cerous sulfate; Described iron salt is at least one in ferric nitrate, iron chloride, iron sulfate; Described cobalt salt is at least one in cobaltous sulfate, cobaltous chloride, cobalt nitrate; Described manganese salt is at least one in manganese sulfate, manganese acetate, manganese carbonate, manganese nitrate; Described nonionic surfactant is TritonX-100 and/or Span-80; Described cosurfactant is the one in n-butyl alcohol, hexanol, n-octyl alcohol; Described organic solvent is hexamethylene or pentane; The mass fraction of described titanium colloidal sol is 10%��30%; Step 1) described in metal salt solution in the concentration of manganese salt be 0.6��1.2mol/L, the concentration of cerium salt or iron salt or cobalt salt is 0.01��0.3mol/L.
4. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterised in that step 2) described in pH adjusting agent be ammonia.
5. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterised in that step 2) described in heating-up temperature be 75��100 DEG C, heat time heating time is 4-8h.
6. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterised in that step 3) described in calcining heat be 400��700 DEG C, calcination time is 1��6h.
7. a support type manganese-based low-temperature denitration catalyst, it is characterised in that: the method described in any one of claim 1-6 is prepared from; Its active component is made up of the one in iron oxides, cerium oxide and cobalt/cobalt oxide and Mn oxide; Carrier is titanium oxide; The content of each oxide is with the mol ratio of elemental metal for Mn:Ti:R=0.015��0.1:1:0.001��0.015, and wherein, R is the one in Ce, Fe, Co element.
8. support type manganese-based low-temperature denitration catalyst according to claim 7, it is characterised in that described Mn oxide is MnO2��Mn2O3And Mn3O4In at least one, described titanium oxide is TiO2, described cerium oxide is CeO2And/or Ce2O3, described iron oxides is Fe3O4And/or Fe2O3, described cobalt/cobalt oxide is CoO, Co3O4And Co2O3In at least one.
9. support type manganese-based low-temperature denitration catalyst according to claim 7, it is characterised in that the active component of described denitrating catalyst is nano-particle, the mean diameter of described nano-particle is 5��20nm.
10. a denitration method for flue gas, it is characterised in that carry out selective catalytic reduction reaction with the support type manganese-based low-temperature denitration catalyst described in any one of claim 7-9, the temperature of described selective catalytic reduction reaction is 80��200 DEG C.
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CN108855051A (en) * 2018-06-20 2018-11-23 北京科技大学 A kind of synthetic method of the two-dimentional Mn oxide for low temperature SCR denitration
CN109304184A (en) * 2018-11-07 2019-02-05 浙江工业大学 A kind of activated carbon loaded iron-manganese-copper denitrating catalyst and its preparation method and application
CN109678193A (en) * 2018-12-25 2019-04-26 沈阳化工大学 A kind of preparation method of ceria nanoparticles
CN109876823A (en) * 2019-03-12 2019-06-14 华东理工大学 A kind of Mn-Fe composite metal catalyst and its preparation method and application
CN111346678A (en) * 2020-03-30 2020-06-30 安徽元琛环保科技股份有限公司 Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst
CN111408365A (en) * 2020-03-30 2020-07-14 上海交通大学 Preparation method of monolithic manganese-based catalyst for low-temperature denitration
CN113649020A (en) * 2021-09-08 2021-11-16 江苏爱尔沃特环保科技有限公司 Low-temperature SCR denitration catalyst loaded with high-entropy oxide and preparation method and application thereof
CN115501748A (en) * 2021-08-31 2022-12-23 嘉兴沃特泰科环保科技股份有限公司 Denitration agent and preparation method thereof
CN115845870A (en) * 2022-11-30 2023-03-28 清华大学深圳国际研究生院 Three-way catalyst and preparation method and application thereof
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CN107051572A (en) * 2017-05-09 2017-08-18 河北工业大学 A kind of manganese based denitration catalyst containing tourmaline and preparation method thereof
CN107376934B (en) * 2017-07-11 2020-09-01 四川大学 Iron oxide pillared layered manganese oxide catalyst and preparation method and application thereof
CN107376934A (en) * 2017-07-11 2017-11-24 四川大学 Pillared layered manganese oxide catalyst of ferriferous oxide and preparation method thereof, application
CN108855051A (en) * 2018-06-20 2018-11-23 北京科技大学 A kind of synthetic method of the two-dimentional Mn oxide for low temperature SCR denitration
CN109304184A (en) * 2018-11-07 2019-02-05 浙江工业大学 A kind of activated carbon loaded iron-manganese-copper denitrating catalyst and its preparation method and application
CN109678193A (en) * 2018-12-25 2019-04-26 沈阳化工大学 A kind of preparation method of ceria nanoparticles
CN109876823A (en) * 2019-03-12 2019-06-14 华东理工大学 A kind of Mn-Fe composite metal catalyst and its preparation method and application
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CN111346678A (en) * 2020-03-30 2020-06-30 安徽元琛环保科技股份有限公司 Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst
CN111408365A (en) * 2020-03-30 2020-07-14 上海交通大学 Preparation method of monolithic manganese-based catalyst for low-temperature denitration
CN115501748A (en) * 2021-08-31 2022-12-23 嘉兴沃特泰科环保科技股份有限公司 Denitration agent and preparation method thereof
CN115501748B (en) * 2021-08-31 2023-05-12 嘉兴沃特泰科环保科技股份有限公司 Denitration agent and preparation method thereof
CN113649020A (en) * 2021-09-08 2021-11-16 江苏爱尔沃特环保科技有限公司 Low-temperature SCR denitration catalyst loaded with high-entropy oxide and preparation method and application thereof
CN113649020B (en) * 2021-09-08 2024-03-05 江苏爱尔沃特环保科技有限公司 Low-temperature SCR denitration catalyst loaded with high-entropy oxide and preparation method and application thereof
CN115888748A (en) * 2022-10-11 2023-04-04 清华大学 Denitration catalyst and preparation method thereof
CN115845870A (en) * 2022-11-30 2023-03-28 清华大学深圳国际研究生院 Three-way catalyst and preparation method and application thereof
CN115845870B (en) * 2022-11-30 2024-03-29 清华大学深圳国际研究生院 Ternary catalyst and preparation method and application thereof

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