CN105457624A - Composite metal oxide catalyst for low temperature denitration and preparation method thereof - Google Patents

Composite metal oxide catalyst for low temperature denitration and preparation method thereof Download PDF

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CN105457624A
CN105457624A CN201510787748.5A CN201510787748A CN105457624A CN 105457624 A CN105457624 A CN 105457624A CN 201510787748 A CN201510787748 A CN 201510787748A CN 105457624 A CN105457624 A CN 105457624A
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许小兵
刘江峰
徐辉
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Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
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Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20769—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • 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 relates to a composite metal oxide catalyst for low temperature denitration, and belongs to the technical field of industrial denitration. The composite metal oxide catalyst for low temperature denitration is characterized by comprising active ingredients containing MoO3, CeO2 and V2O5, and a carrier of TiO2. The active ingredients and the carrier are proportioned according to the following weight ratio: 3-10 parts of MoO3, 1-5 parts of CeO2, 1-5 parts of V2O5, and 100 parts of TiO2. Through the above technical scheme, the active ingredients of MoO3, CeO2 and V2O5 are supported by TiO2 to form a MoO3-CeO2-V2O5 / TiO2 composite metal oxide catalyst for low temperature denitration. The molybdenum-based catalyst has good low-temperature catalytic activity; and CeO2 as an active auxiliary agent not only effectively suppresses SO2 from converting to SO3 to reduce the risk of catalyst clogging and poisoning, but also broadens the active window of the catalyst, so as to reach significant beneficial effects. The invention also relates to a preparation method of the catalyst. The method reaches a stable denitration efficiency of above 90%, and has excellent denitration effect.

Description

A kind of composite metal oxide low-temperature denitration catalyst and preparation method thereof
Technical field
The present invention relates to a kind of denitrating catalyst, particularly a kind of composite metal oxide low-temperature denitration catalyst, the invention still further relates to a kind of preparation method of this catalyst, belongs to industrial denitration technology field.
Background technology
Improving constantly along with industrialization degree; the material life water product of people have also been obtained great improvement; but because people prepare not enough to the negative effect of industrial development; the contaminated problem of the environment causing people to depend on for existence annoyings; in recent years, air pollution problems inherent is outstanding day by day, how to administer these contamination phenomenon; from source, it is controlled, become the important topic of environmental protection.
Nitrogen oxide (NO x) be one of main pollutant in air, it is mainly derived from the exhaust emissions of Industrial Boiler as coal-burning power plant, glass furnace, cement kiln etc., nitrogen oxide is the main contributor causing the environmental problems such as haze, acid rain, photochemical fog, it also can't neglect the direct injury of human body, human body sucks the direct insulting respiratory system of meeting, cause breathing problem, even can cause cancer time serious.
At present, SCR denitration technology is the core technology guaranteeing that nitrogen oxide is removed, but the activation temperature of SCR denitration is probably more than 300 DEG C, thus in actual application, SCR reactor is generally arranged immediately after the boilers, to meet the demand to the activation temperature of SCR denitration.But the equipment requirement of this set-up mode to reactor is high, and input cost is high, and SCR denitration is direct and undressed smoke contacts in boiler, catalyst self easily affects by dust and oxysulfide, and cause catalytic efficiency lower, catalyst body easily blocks with poisoning.
Summary of the invention
For solving problems of the prior art, the invention provides a kind of composite metal oxide low-temperature denitration catalyst, concrete technical scheme is as follows:
A kind of composite metal oxide low-temperature denitration catalyst, comprise active component and carrier, it is characterized in that, described active component comprises MoO 3, CeO 2, V 2o 5, described carrier is TiO 2, described active component and carrier are according to following portions by weight:
MoO 33 parts ~ 10 parts
CeO 21 part ~ 5 parts
V 2o 51 part ~ 5 parts
TiO 2100 parts
Carry out proportioning to obtain.
Technique scheme passes through MoO 3, CeO 2and V 2o 5the active component of common composition, at TiO 2load under form MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst, this catalyst with base of molybdenum has good low-temperature catalytic activity, wherein CeO 2as coagent, not only effectively suppress SO 2change into SO 3, reduce catalyst blockage and poisoning risk, beneficial effect is remarkable; And widened the active window of catalyst, catalytic activity temperature is at 130 DEG C ~ 370 DEG C, the arrangement mode of SCR reactor can be changed, after reactor is arranged on desulfurization and dedusting, now lower flue-gas temperature just in time falls in the active window of catalyst of the present invention, effectively reduce equipment cost, worth industry is applied.
Present invention also offers a kind of preparation method of above-mentioned composite metal oxide low-temperature denitration catalyst, concrete technical scheme is as follows:
A preparation method for composite metal oxide low-temperature denitration catalyst, comprises the following steps: step one, the preparation of precursor solution; Step 2, the load of active component; It is characterized in that,
Described step one is divided into following three steps:
(1) solution A preparation, the soluble salt presoma of Mo, Ce, V is taken according to the weight fraction of active component, wherein the parts by weight of Mo, Ce, V are followed successively by 3 parts ~ 10 parts, 1 part ~ 5 parts, 1 part ~ 5 parts, joined in the solvent containing cosolvent, heating water bath, be stirred to solid to dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, mixes solution A with solution B, obtains homogeneous mixed solution after ultrasonic process;
Described step 2 is divided into following three steps:
(1) metal salt precipitate, slowly adds precipitating reagent, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through oven drying, high-temperature roasting by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
As the improvement of technique scheme, in the solution A preparation of described step one, the soluble salt presoma of Mo, Ce, V is respectively ammonium heptamolybdate, cerous nitrate, ammonium metavanadate.
As the improvement of technique scheme, in the solution A preparation of described step one, solvent is deionized water or ethylene glycol.
As the improvement of technique scheme, in the solution A preparation of described step one, cosolvent is MEA or ammoniacal liquor.
As the improvement of technique scheme, in the solution A preparation of described step one, water bath heating temperature is 80 DEG C ~ 100 DEG C, and water bath time is 1h ~ 4h.
As the improvement of technique scheme, in the mixed solution preparation of described step one, supersonic frequency is 10kHz ~ 100kHz, and ultrasonic time is 2h ~ 12h.
As the improvement of technique scheme, in the metal salt precipitate of described step 2, precipitating reagent is NaOH or urea.
As the improvement of technique scheme, in the drying of described step 2, roasting, baking temperature is 60 DEG C ~ 110 DEG C, and drying time is 12h ~ 24h.
As the improvement of technique scheme, in the drying of described step 2, roasting, sintering temperature is 300 DEG C ~ 600 DEG C, and temperature retention time is 4h ~ 12h.
Technique scheme passes through the standby composite metal oxide low temperature catalyst of chemical codeposition legal system, and have higher specific area, denitration efficiency can be stabilized in more than 90%, and denitration effect is excellent.
Detailed description of the invention
The invention provides a kind of composite metal oxide low-temperature denitration catalyst, comprise active component and carrier, described active component comprises MoO 3, CeO 2, V 2o 5, described carrier is TiO 2, described active component and carrier are according to following portions by weight:
MoO 33 parts ~ 10 parts
CeO 21 part ~ 5 parts
V 2o 51 part ~ 5 parts
TiO 2100 parts
Carry out proportioning to obtain.
Technique scheme passes through MoO 3, CeO 2and V 2o 5the active component of common composition, at TiO 2load under form MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst, this catalyst with base of molybdenum has good low-temperature catalytic activity, wherein CeO 2as coagent, not only effectively suppress SO 2change into SO 3reduce catalyst blockage and poisoning risk, and widened the active window of catalyst, catalytic activity temperature is at 130 DEG C ~ 370 DEG C, the arrangement mode of SCR reactor can be changed, after reactor is arranged on desulfurization and dedusting, now lower flue-gas temperature just in time falls in the active window of catalyst of the present invention, effectively reduces equipment cost.
Present invention also offers a kind of preparation method of above-mentioned composite metal oxide low-temperature denitration catalyst, comprise the following steps: step one, the preparation of precursor solution; Step 2, the load of active component; It is characterized in that,
Described step one is divided into following three steps:
(1) solution A preparation, the soluble salt presoma of Mo, Ce, V is taken according to the weight fraction of active component, wherein the parts by weight of Mo, Ce, V are followed successively by 3 parts ~ 10 parts, 1 part ~ 5 parts, 1 part ~ 5 parts, joined in the solvent containing cosolvent, heating water bath, be stirred to solid to dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, mixes solution A with solution B, obtains homogeneous mixed solution after ultrasonic process;
Described step 2 is divided into following three steps:
(1) metal salt precipitate, slowly adds precipitating reagent, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through oven drying, high-temperature roasting by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Said method passes through the standby composite metal oxide low temperature catalyst of chemical codeposition legal system, and have higher specific area, denitration efficiency can be stabilized in more than 90%, and denitration effect is excellent.
Further, in the solution A preparation of described step one, the soluble salt presoma of Mo, Ce, V is respectively ammonium heptamolybdate, cerous nitrate, ammonium metavanadate; In the solution A preparation of described step one, solvent is deionized water or ethylene glycol; In the solution A preparation of described step one, cosolvent is MEA or ammoniacal liquor; In the solution A preparation of described step one, water bath heating temperature is 80 DEG C ~ 100 DEG C, and water bath time is 1h ~ 4h; In the mixed solution preparation of described step one, supersonic frequency is 10kHz ~ 100kHz, and ultrasonic time is 2h ~ 12h; In the metal salt precipitate of described step 2, precipitating reagent is NaOH or urea; In the drying of described step 2, roasting, baking temperature is 60 DEG C ~ 110 DEG C, and drying time is 12h ~ 24h; In the drying of described step 2, roasting, sintering temperature is 300 DEG C ~ 600 DEG C, and temperature retention time is 4h ~ 12h.
Be introduced below in conjunction with specific embodiment.
Embodiment one
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 5 parts of ammonium heptamolybdates, 2 parts of cerous nitrates, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 100kHz ultrasonic process 4h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment two
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 5 parts of ammonium heptamolybdates, 1 part of cerous nitrate, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 5h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment three
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 5 parts of ammonium heptamolybdates, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 5h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment four
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 3 parts of ammonium heptamolybdates, 2 parts of cerous nitrates, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 5h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment five
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 1 part of ammonium heptamolybdate, 2 parts of cerous nitrates, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 5h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment six
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 2 parts of cerous nitrates, 2 parts of ammonium metavanadates, joined in the deionized water containing MEA, 80 DEG C of heating water bath 2h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 5h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds urea, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 105 DEG C of oven drying 12h and 500 DEG C of high-temperature roasting 5h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment seven
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 3 parts of ammonium heptamolybdates, 1 part of cerous nitrate, 1 part of ammonium metavanadate, joined the ethylene glycol containing ammoniacal liquor, 90 DEG C of heating water bath 4h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10kHz ultrasonic process 12h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds NaOH, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 110 DEG C of oven drying 12h and 600 DEG C of high-temperature roasting 4h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Embodiment eight
MoO is carried out according to following steps 3-CeO 2-V 2o 5/ TiO 2the preparation of composite metal oxide low-temperature denitration catalyst, step one, the preparation of precursor solution:
(1) solution A preparation, take 10 parts of ammonium heptamolybdates, 5 parts of cerous nitrates, 5 parts of ammonium metavanadates, joined the ethylene glycol containing ammoniacal liquor, 100 DEG C of heating water bath 1h, are stirred to solid and dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, solution A is mixed with solution B, 10KHz ultrasonic process 2h, after obtain homogeneous mixed solution;
Step 2, the load of active component:
(1) metal salt precipitate, slowly adds NaOH, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through 60 DEG C of oven drying 24h and 300 DEG C of high-temperature roasting 12h by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
Fixed bed activity rating is tested the catalyst activity of eight embodiments of the present invention respectively, and test event comprises: NOx removal efficiency, SO 2/ SO 3oxygenation efficiency and temperature when reaching denitration rate 80%.Test condition is: simulated flue gas flow is 0.8Nm 3/ h; Simulated flue gas composition is 6%O 2, 600ppmNH 3, 600ppmNO, 0.1%SO 2; Range of measuring temp is 100 DEG C ~ 400 DEG C.Test result is as shown in table 1:
The catalytic activity result of table 1 catalyst
Embodiment One Two Three Four Five Six Seven Eight
Active component MoO 3Content (part) 5 5 5 3 1 0 3 10
Active component CeO 2Content (part) 2 1 0 2 2 2 1 5 6 -->
Active component V 2O 5Content (part) 2 2 2 2 2 2 1 5
NO xRemoval efficiency (%) 97 95 94 96 93 91 90 96
SO 2Conversion ratio (%) 1.6 2.3 3.3 2.1 1.9 1.8 1.9 1.7
Temperature (DEG C) when reaching denitration rate 80% 130 140 140 180 240 360 192 135
Draw by testing above, active component MoO in catalyst 3content will have influence on temperature when catalyst reaches denitration rate 80%, and along with the raising of Mo content, when denitration rate reaches 80%, temperature progressively declines and maintains near 130 DEG C, makes catalyst possess good low-temperature catalytic activity; Found through experiments, active component CeO simultaneously 2add and effectively can suppress SO 2conversion, thus reduce the risk of catalyst poisoning; This experiment NO on the whole xremoval efficiency remains on more than 90%, and denitration effect is excellent.

Claims (10)

1. a composite metal oxide low-temperature denitration catalyst, comprises active component and carrier, it is characterized in that, described active component comprises MoO 3, CeO 2, V 2o 5, described carrier is TiO 2, described active component and carrier are according to following portions by weight:
MoO 33 parts ~ 10 parts
CeO 21 part ~ 5 parts
V 2o 51 part ~ 5 parts
TiO 2100 parts
Carry out proportioning to obtain.
2. a preparation method for a kind of composite metal oxide low-temperature denitration catalyst according to claim 1, comprises the following steps: step one, the preparation of precursor solution; Step 2, the load of active component; It is characterized in that,
Described step one is divided into following three steps:
(1) solution A preparation, the soluble salt presoma of Mo, Ce, V is taken according to the weight fraction of active component, wherein the parts by weight of Mo, Ce, V are followed successively by 3 parts ~ 10 parts, 1 part ~ 5 parts, 1 part ~ 5 parts, joined in the solvent containing cosolvent, heating water bath, be stirred to solid to dissolve completely, obtain solution A;
(2) solution B preparation, takes the Detitanium-ore-type TiO of 100 parts 2carrier, slowly adds in deionized water solution, stirs and is mixed with uniform emulsion, obtain solution B;
(3) mixed solution preparation, mixes solution A with solution B, obtains homogeneous mixed solution after ultrasonic process;
Described step 2 is divided into following three steps:
(1) metal salt precipitate, slowly adds precipitating reagent, treats that slaine all precipitates in the mixed solution that step one obtains;
(2) filtration washing, retains sediment micro porous filtration, and washing is neutral to PH;
(3) dry, roasting, passes through oven drying, high-temperature roasting by the sediment filtered, obtained MoO 3-CeO 2-V 2o 5/ TiO 2composite metal oxide low-temperature denitration catalyst.
3. preparation method as claimed in claim 2, is characterized in that, in the solution A preparation of described step one, the soluble salt presoma of Mo, Ce, V is respectively ammonium heptamolybdate, cerous nitrate, ammonium metavanadate.
4. preparation method as claimed in claim 2, is characterized in that, in the solution A preparation of described step one, solvent is deionized water or ethylene glycol.
5. preparation method as claimed in claim 2, is characterized in that, in the solution A preparation of described step one, cosolvent is MEA or ammoniacal liquor.
6. preparation method as claimed in claim 2, is characterized in that, in the solution A preparation of described step one, water bath heating temperature is 80 DEG C ~ 100 DEG C, and water bath time is 1h ~ 4h.
7. preparation method as claimed in claim 2, is characterized in that, in the mixed solution preparation of described step one, supersonic frequency is 10kHz ~ 100kHz, and ultrasonic time is 2h ~ 12h.
8. preparation method as claimed in claim 2, it is characterized in that, in the metal salt precipitate of described step 2, precipitating reagent is NaOH or urea.
9. preparation method as claimed in claim 2, is characterized in that, in the drying of described step 2, roasting, baking temperature is 60 DEG C ~ 110 DEG C, and drying time is 12h ~ 24h.
10. preparation method as claimed in claim 2, is characterized in that, in the drying of described step 2, roasting, sintering temperature is 300 DEG C ~ 600 DEG C, and temperature retention time is 4h ~ 12h.
CN201510787748.5A 2015-11-17 2015-11-17 Composite metal oxide catalyst for low temperature denitration and preparation method thereof Pending CN105457624A (en)

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CN110639501A (en) * 2019-11-06 2020-01-03 山东博霖环保科技发展有限公司 SCR denitration catalyst and preparation method thereof
CN111203208A (en) * 2020-01-09 2020-05-29 华侨大学 Low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof
CN111495174A (en) * 2019-01-30 2020-08-07 国家能源投资集团有限责任公司 Denitration catalyst and preparation method and application thereof
CN112808263A (en) * 2020-12-30 2021-05-18 大唐南京环保科技有限责任公司 Low SO2/SO3Denitration catalyst with conversion rate and preparation method thereof
WO2021092829A1 (en) * 2019-11-14 2021-05-20 江西新科环保股份有限公司 Method for preparing denitration catalyst for flue gas of glass furnace
CN115709062A (en) * 2022-10-11 2023-02-24 清华大学 Denitration catalyst and preparation method thereof

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CN103252231A (en) * 2013-05-02 2013-08-21 易能(中国)环保科技有限公司 Denitration catalyst and preparation method thereof

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN111495174A (en) * 2019-01-30 2020-08-07 国家能源投资集团有限责任公司 Denitration catalyst and preparation method and application thereof
CN110508273A (en) * 2019-07-26 2019-11-29 华侨大学 A kind of low temperature vanadium titanium-based SCR denitration and preparation method thereof
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CN111203208A (en) * 2020-01-09 2020-05-29 华侨大学 Low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof
CN112808263A (en) * 2020-12-30 2021-05-18 大唐南京环保科技有限责任公司 Low SO2/SO3Denitration catalyst with conversion rate and preparation method thereof
CN115709062A (en) * 2022-10-11 2023-02-24 清华大学 Denitration catalyst and preparation method thereof
CN115709062B (en) * 2022-10-11 2024-02-13 清华大学 Denitration catalyst and preparation method thereof

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