CN105618032B - Support type manganese-based low-temperature denitration catalyst and preparation method thereof - Google Patents

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

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CN105618032B
CN105618032B CN201610035584.5A CN201610035584A CN105618032B CN 105618032 B CN105618032 B CN 105618032B CN 201610035584 A CN201610035584 A CN 201610035584A CN 105618032 B CN105618032 B CN 105618032B
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manganese
salt
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CN105618032A (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 present invention is that the preparation method specifically includes following steps on a kind of support type manganese-based low-temperature denitration catalyst and preparation method thereof：1) by cerium salt or molysite or cobalt salt and manganese salt formation metal salt solution soluble in water, nonionic surfactant, cosurfactant and organic solvent is added in metal salt solution, stirred to clarify, obtains microemulsion；Described water, nonionic surfactant, the molar ratio of cosurfactant and organic solvent are 1：0.03~0.6：0.1~1.2：1~5；2) titanium colloidal sol is added in described microemulsion, stirring, it is 8~11 then to adjust its pH value with pH adjusting agent, heating, obtains xerogel；3) by described xerogel grinding, calcining, denitrating catalyst is obtained.The preparation method of the present invention is by catalyst activity component in whole carrier TiO2In it is dispersed, realize catalyst activity component and be all deposited on carrier, the denitrating catalyst low temperature active temperature range is wide, and catalytic activity is high.

Description

Support type manganese-based low-temperature denitration catalyst and preparation method thereof
Technical field
The present invention relates to a kind of catalyst, more particularly to a kind of support type manganese-based low-temperature denitration catalyst and its preparation side Method.
Background technology
Nitrogen oxides (NOx) be one of main atmosphere pollution, be the problems such as causing acid rain, secondary fine particle before Body thing.In view of NOxTo harm existing for ecological environment, NO is controlledxGeneration and discharge the problem of being particularly significant.At present, control NOxThe technology of discharge refers mainly to low NOxCombustion technology and flue gas NOxRemoving sulfuldioxide, and in NOxIn removing sulfuldioxide, selective catalysis It is the gas denitrifying technology being most widely used in the world to reduce (SCR), and denitration rate can reach 90%.
At present, manganese base (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 uniform mixing of the multicomponent catalyst on carrier, the catalyst activity component during post processing It can not be carried on completely on carrier, therefore cause the activity of catalyst preferably to play a role.Prior art proposes one Kind manganese systems support type low-temperature denitration catalyst, the catalyst is using titanyl compound as carrier, using the oxide of manganese as active component, Using the oxide of tungsten as co-catalyst, it is prepared by infusion process.Dispersiveness of the active component of the catalyst on carrier It is poor, cause its catalytic activity poor.
The content of the invention
It is a primary object of the present invention to, there is provided a kind of new support type manganese-based low-temperature denitration catalyst and its preparation side Method, technical problem to be solved are can to improve catalytic activity, expand low temperature active temperature range, thus more suitable for It is practical.
The object of the invention to solve the technical problems is realized using following technical scheme.Itd is proposed according to the present invention A kind of support type manganese-based low-temperature denitration catalyst preparation method, it is characterised in that：Specifically comprise the steps of：
1) by cerium salt or molysite or cobalt salt and manganese salt formation metal salt solution soluble in water, by nonionic surfactant, Cosurfactant and organic solvent are added in metal salt solution, are stirred to clarify, and obtain microemulsion；Described water, it is non-from The molar ratio of sub- surfactant, cosurfactant and organic solvent is 1：0.03~0.6：0.1~1.2：1~5；
2) titanium colloidal sol is added in described microemulsion, stirring, it is 8~11 then to adjust its pH value with pH adjusting agent, Heating, obtains xerogel；
3) by described xerogel grinding, calcining, denitrating catalyst is obtained.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, the preparation method of foregoing support type manganese-based low-temperature denitration catalyst, wherein described cerium salt or molysite Or cobalt salt and manganese salt, the dosage of titanium colloidal sol are using the mol ratio of elemental metal as Mn：Ti：R=0.015~0.1：1：0.001~ One kind in 0.015, R Ce, Fe, Co element.
Preferably, the preparation method of foregoing support type manganese-based low-temperature denitration catalyst, wherein described cerium salt is nitric acid At least one of cerium, cerium chloride, cerous sulfate；Described molysite is at least one of ferric nitrate, iron chloride, ferric sulfate；Institute The cobalt salt stated is at least one of cobaltous sulfate, cobalt chloride, cobalt nitrate；Described manganese salt be manganese sulfate, manganese acetate, manganese carbonate, At least one of manganese nitrate；Described nonionic surfactant is Triton X-100 and/or Span-80；Described helps Surfactant is one kind in n-butanol, n-hexyl alcohol, n-octyl alcohol；Described organic solvent is hexamethylene or pentane；It is described Titanium colloidal sol mass fraction be 10%~30%；In metal salt solution described in step 1) concentration of manganese salt be 0.6~ 1.2mol/L, cerium salt or the concentration of molysite or cobalt salt are 0.01~0.3 mol/L.
Preferably, the preparation method of foregoing support type manganese-based low-temperature denitration catalyst, the pH regulations described in step 2) Agent is ammoniacal liquor.
Preferably, the preparation method of foregoing support type manganese-based low-temperature denitration catalyst, the heating temperature described in step 2) Spend for 75~100 DEG C, heat time 4-8h.
Preferably, the preparation method of foregoing support type manganese-based low-temperature denitration catalyst, the calcining temperature described in step 3) Spend for 400~700 DEG C, calcination time is 1~6h.
The object of the invention to solve the technical problems is also realized using following technical scheme.Itd is proposed according to the present invention A kind of support type manganese-based low-temperature denitration catalyst, be prepared by method of the present invention；Its active component is aoxidized by iron One kind and Mn oxide composition in thing, cerium oxide and cobalt/cobalt oxide；Carrier is titanium oxide；The content of each oxide is with gold The mol ratio for belonging to element meter is Mn：Ti：R=0.015~0.1：1：0.001~0.015, wherein, in R Ce, Fe, Co element One kind.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, foregoing support type manganese-based low-temperature denitration catalyst, wherein described Mn oxide is MnO2、Mn2O3 And Mn3O4At least one of, described titanium oxide is TiO2, described cerium oxide is CeO2And/or Ce2O3, it is described Ferriferous oxide is Fe3O4And/or Fe2O3, described cobalt/cobalt oxide is CoO, Co3O4And Co2O3At least one of.
Preferably, foregoing support type manganese-based low-temperature denitration catalyst, wherein the active component of described denitrating catalyst For nano particle, the average grain diameter of described nano particle is 5~20nm.
Selective catalytic reduction reaction, described choosing are carried out to support type manganese-based low-temperature denitration catalyst prepared by the present invention The temperature of selecting property catalytic reduction reaction is 80~200 DEG C.
By above-mentioned technical proposal, under support type manganese-based low-temperature denitration catalyst of the present invention and preparation method thereof at least has Row advantage：
1. the present invention proposes a kind of reverse microemulsion system being made up of nonionic surfactant/water, catalysis is formd Agent active component nano particle, by controlling reaction condition not only to reduce the reunion of catalyst activity component nano particle, The size of nano particle can also be controlled.
2. the present invention is by The Microemulsion-gel Method by catalyst activity component in whole carrier TiO2In it is dispersed, realize Catalyst activity component is all deposited on carrier, and catalyst has a relatively low light-off temperature, higher catalytic activity and compared with Wide temperature window.
3rd, the catalyst of same composition of the catalyst of the present invention than being prepared by the use of titanium dioxide powder as carrier has higher Low-temperature denitration activity.
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 specification, described in detail below with presently preferred embodiments of the present invention as after.
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with Preferred embodiment, to according to support type manganese-based low-temperature denitration catalyst proposed by the present invention and preparation method thereof its specific embodiment party Formula, feature and its effect, describe in detail as after.In the following description, what different " embodiment " or " embodiment " referred to differs Surely it is the same embodiment.In addition, the special characteristic or feature in one or more embodiments can be combined by any suitable form.
Embodiment 1
1) cerous nitrate of 1.79g manganese nitrates and 0.87g is dissolved in the mixed solution that manganese salt and cerium salt are formed in 10mL water, 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and cerium salt；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06： 0.15：1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 10 that water, which adjusts its pH value, is placed in 85 DEG C of heating 5h in baking oven, obtains xerogel；
3) xerogel is ground, 500 DEG C of calcining 3h, obtains CeO2-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CeO2-MnOxNano particle, the average grain diameter of nano particle is 11nm.Should The ratio surface of denitrating catalyst is 104m2/g。
Embodiment 2
1) 1.79g manganese nitrates and 0.33g iron chloride are dissolved in the mixed solution that manganese salt and molysite are formed in 10mL water, will 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and molysite；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06： 0.15：1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 10 that water, which adjusts its pH value, is placed in 87 DEG C of heating 5h in baking oven, obtains xerogel；
3) xerogel is ground, 550 DEG C of calcining 3h, obtains Fe2O3-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is Fe2O3-MnOxNano particle, the average grain diameter of nano particle is 6nm.Should The ratio surface of denitrating catalyst is 87m2/g。
Embodiment 3
1) 1.79g manganese nitrates and 0.26 cobalt chloride are dissolved in the mixed solution that manganese salt and cobalt salt are formed in 10mL water, will 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and cobalt salt；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06：0.15：1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 10 that water, which adjusts its pH value, is placed in 90 DEG C of heating 6h in baking oven, obtains xerogel；
3) xerogel is ground, 580 DEG C of calcining 3h, obtains CoO-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CoO-MnOxNano particle, the average grain diameter of nano particle is 16nm.Should The ratio surface of denitrating catalyst is 63m2/g。
Embodiment 4
1) 1.39g manganese acetates and 0.44g cerous nitrates are dissolved in the mixed solution that manganese salt and cerium salt are formed in 10mL water, will 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and cerium salt；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06： 0.15：1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 9 that water, which adjusts its pH value, is placed in 85 DEG C of heating 4h in baking oven, obtains xerogel；
3) xerogel is ground, 600 DEG C of calcining 3h, obtains CeO2-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CeO2-MnOxNano particle, the average grain diameter of nano particle is 14nm.Should The ratio surface of denitrating catalyst is 96m2/g。
Embodiment 5
1) 1.39g manganese acetates and 0.4g ferric sulfate solutions are formed to the mixed solution of manganese salt and molysite in 10mL water, will 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and molysite；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06：0.15： 1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 8 that water, which adjusts its pH value, is placed in 90 DEG C of heating 6h in baking oven, obtains xerogel；
3) xerogel is ground, 630 DEG C of calcining 4h, obtains Fe2O3-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is Fe2O3-MnOxNano particle, the average grain diameter of nano particle is 19nm.Should The ratio surface of denitrating catalyst is 67m2/g。
Embodiment 6
1) 1.39g manganese acetates and 0.16g cobaltous sulfates are dissolved in the mixed solution that manganese salt and cobalt salt are formed in 10mL water, will 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and cobalt salt；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06： 0.15：1.5；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 9 that water, which adjusts its pH value, is placed in 90 DEG C of heating 5h in baking oven, obtains xerogel；
3) xerogel is ground, 600 DEG C of calcining 5h, obtains CoO-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CoO-MnOxNano particle, the average grain diameter of nano particle is 13nm.Should The ratio surface of denitrating catalyst is 51m2/g。
Embodiment 7
1) 1.79g manganese nitrates and 0.87g cerous sulfates are dissolved in the mixed solution that manganese salt and cerium salt are formed in 10mL water, will 71.89g Trion X-100,17g n-hexyl alcohols and 192mL pentanes is added in above-mentioned mixed solution, is stirred to clarify, is obtained To manganese containing salt and the microemulsion of cerium salt；Wherein, the mol ratio 1 of water, Trion X-100, n-hexyl alcohol, pentane：0.2：0.3： 3.0；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 10 that water, which adjusts its pH value, is placed in 100 DEG C of heating 8h in baking oven, obtains xerogel；
3) xerogel is ground, 500 DEG C of calcining 6h, obtains CeO2-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CeO2-MnOxNano particle, the average grain diameter of nano particle is 18nm.Should The ratio surface of denitrating catalyst is 72m2/g。
Embodiment 8
1) 1.79g manganese nitrates and 0.87g cerous sulfates are dissolved in the mixed solution that manganese salt and cerium salt are formed in 10mL water, will 21.57g Trion X-100,7.22g n-octyl alcohols and 108mL hexamethylenes is added in above-mentioned mixed solution, is stirred to clarify, Obtain the microemulsion of manganese containing salt and cerium salt；Wherein, the mol ratio 1 of water, Trion X-100, n-octyl alcohol, hexamethylene：0.06： 0.10：1.8；
2) 91.7g titaniums colloidal sol (mass fraction 18.0%) is added in above-mentioned microemulsion, stirs 1h, then use ammonia It is 11 that water, which adjusts its pH value, is placed in 90 DEG C of heating 6h in baking oven, obtains xerogel；
3) xerogel is ground, 650 DEG C of calcining 5h, obtains CeO2-MnOx/TiO2Denitrating catalyst.
The active component of the denitrating catalyst is CeO2-MnOxNano particle, the average grain diameter of nano particle is 20nm.Should The ratio surface of denitrating catalyst is 96m2/g。
Comparative example
1) cerous nitrate of 1.79g manganese nitrates and 0.87g is dissolved in the mixed solution that manganese salt and cerium salt are formed in 10mL water, 7.17g Span-80,10.75g Trion X-100,8.5g n-hexyl alcohols and 90mL hexamethylenes are added to above-mentioned mixed solution In, stir to clarify, obtain the microemulsion of manganese containing salt and cerium salt；Wherein, water, mixed surfactant, n-hexyl alcohol, hexamethylene Mol ratio 1：0.06：0.15：1.5；
2) 16.5g titanium dioxides are added in above-mentioned microemulsion, stir 1h, it is 10 then to adjust its pH value with ammoniacal liquor, after Continuous stirring, adds acetone, stands, and filters, precipitation is washed with a large amount of deionized waters and ethanol, dries；
3) product of drying is calcined 3h at 500 DEG C.
The ratio surface of the comparative example catalyst is 41m2/g
Catalyst made from embodiment 1-8 and comparative example is reacted for low-temperature selective catalytic reduction denitration, reacts bar Part and Activity Results are shown in Table 1.
Catalyst performance evaluation：Activity experiment is carried out on self-control catalyst test platform, and catalyst filling amount is 5ml, Ammonia nitrogen ratio is 1:1, O2Concentration is 6% (V/V), GHSV (gas space velocity per hour)=10000h-1Flue gas, determine 80 respectively DEG C, the NO conversion ratios of 100 DEG C, 150 DEG C, 200 DEG C etc. 4 temperature spots.When temperature of reactor is stabilized to a certain temperature spot, open Beginning is passed through simulated flue gas, after reacting 10min, using in gas before and after flue gas analyzer (Testo350, Germany) measure reaction NO concentration, each temperature spot test constantly time are 15min, are averaged, and NO conversion ratios, i.e. denitration rate are calculated according to formula 1.
NO conversion ratios=[(NOin-NOout)/NOin] × 100% (formula 1)
The catalyst low-temperature selective catalytic reduction denitration reaction test Activity Results of table 1.
Note：Simulated flue gas forms：600ppm or so NO, 600ppm or so NH3, O2Intrinsic standoff ratio 6%, remaining is balance Gas N2, air speed 10000h-1。
Found by the contrast of embodiment and comparative example, the ratio surface of the denitrating catalyst prepared using the precipitation method, which is less than, adopts The ratio surface of the denitrating catalyst prepared with The Microemulsion-gel Method, and the denitration rate in 80~200 DEG C of temperature ranges is less than 70%.Using titanium colloidal sol as catalyst prepared by carrier urging than the same composition that is prepared by the use of titanium dioxide powder as carrier Agent has higher low-temperature denitration activity.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, according to Any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within this hair In the range of bright technical scheme.

Claims (10)

  1. A kind of 1. preparation method of support type manganese-based low-temperature denitration catalyst, it is characterised in that：Specifically comprise the steps of：
    1) by cerium salt or molysite or cobalt salt and manganese salt formation metal salt solution soluble in water, by nonionic surfactant, table is helped Face activating agent and organic solvent are added in metal salt solution, are stirred to clarify, and obtain microemulsion；Described water, nonionic table The molar ratio of face activating agent, cosurfactant and organic solvent is 1：0.03~0.6：0.1~1.2：1~5；
    2) titanium colloidal sol is added in described microemulsion, stirring, it is 8~11 then to adjust its pH value with pH adjusting agent, heating, Obtain xerogel；
    3) by described xerogel grinding, calcining, denitrating catalyst is obtained.
  2. 2. the preparation method of support type manganese-based low-temperature denitration catalyst according to claim 1, it is characterised in that described Cerium salt or molysite or cobalt salt and manganese salt, the dosage of titanium colloidal sol are using the mol ratio of elemental metal as Mn：Ti：R=0.015~0.1： 1：One kind in 0.001~0.015, R Ce, Fe, Co element.
  3. 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 of cerous nitrate, cerium chloride, cerous sulfate；Described molysite is ferric nitrate, iron chloride, in ferric sulfate extremely Few one kind；Described cobalt salt is at least one of cobaltous sulfate, cobalt chloride, cobalt nitrate；Described manganese salt is manganese sulfate, acetic acid At least one of manganese, manganese carbonate, manganese nitrate；Described nonionic surfactant is Triton X-100 and/or Span- 80；Described cosurfactant is one kind in n-butanol, n-hexyl alcohol, n-octyl alcohol；Described organic solvent be hexamethylene or Pentane；The mass fraction of described titanium colloidal sol is 10%~30%；Manganese salt is dense in metal salt solution described in step 1) Spend for 0.6~1.2mol/L, cerium salt or the concentration of molysite or cobalt salt are 0.01~0.3mol/L.
  4. 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 ammoniacal liquor.
  5. 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 4-8h.
  6. 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 kind of 7. support type manganese-based low-temperature denitration catalyst, it is characterised in that：As the method system described in claim any one of 1-6 It is standby to form；Its active component is made up of one kind in ferriferous oxide, cerium oxide and cobalt/cobalt oxide and Mn oxide；Carrier is titanium Oxide；The content of each oxide is using the mol ratio of elemental metal as Mn：Ti：R=0.015~0.1：1：0.001~ 0.015, wherein, one kind in R Ce, Fe, Co element.
  8. 8. support type manganese-based low-temperature denitration catalyst according to claim 7, it is characterised in that described Mn oxide is MnO2、Mn2O3And Mn3O4At least one of, described titanium oxide is TiO2, described cerium oxide is CeO2And/or Ce2O3, described ferriferous oxide is Fe3O4And/or Fe2O3, described cobalt/cobalt oxide is CoO, Co3O4And Co2O3In at least one Kind.
  9. 9. support type manganese-based low-temperature denitration catalyst according to claim 7, it is characterised in that described denitrating catalyst Active component be nano particle, the average grain diameter of described nano particle is 5~20nm.
  10. 10. a kind of denitration method for flue gas, it is characterised in that taken off with the support type manganese-based low-temperature described in claim any one of 7-9 Denox catalyst carries out selective catalytic reduction reaction, and the temperature of described selective catalytic reduction reaction is 80~200 DEG C.
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