CN102600861B - For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone - Google Patents
For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone Download PDFInfo
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Abstract
The present invention relates to a kind of manganese base composite oxidate Catalysts and its preparation method for catalytic decomposition ozone.Described catalyst comprises Mn oxide and at least one transition metal oxide.Described preparation method is sluggish precipitation or hydrothermal synthesis method.The present invention adopts nontoxic raw material, prepared by simple method and have that catalytic activity is high, anti humility performance good, the manganese base composite oxidate catalyst of catalytic decomposition ozone amount high, be suitable for the catalytic decomposition of the ozone that catalytic decomposition produces at water or air-treatment and modern industry and household electrical appliance.
Description
Technical field
The present invention relates to a kind of catalyst, be specifically related to a kind of manganese base composite oxidate catalyst for catalytic decomposition ozone, particularly a kind of manganese base composite oxidate Catalysts and its preparation method of the ozone produced at water or air-treatment and modern industry and household electrical appliance for catalytic decomposition.
Background technology
Ozone (O
3) and oxygen (O
2) be the allotrope of oxygen element, under normal temperature, ozone (O
3) be a kind of lavender gas having the instability of special fishy smell.In recent years, due to its strong oxidizing property, ozone, as disinfectant, bactericide and deodorant, obtains increasingly extensive application in the treatment of waste water.But the residual ozone do not consumed after process water will be discharged into contaminated environment in air.Along with the perfect raising of modern office equipment, the machines such as a large amount of duplicator, printing machine, facsimile machine, and dust catcher, air cleaner use, produced ozone by corona discharge, ozone in surrounding environment is accumulated gradually, harmful during excessive concentration.These ozone are not processed directly enters air, produces harm to various life entity and living environment thereof.Ozone can the respiratory tract of intense stimulus people, causes abscess of throat, cough uncomfortable in chest, causes bronchitis and pulmonary emphysema; The neurotoxic of people can be caused, dizziness headache, visual impairment, to be losing one's memory; Destruction can be played to the vitamin E in human body skin, cause the skin of people wrinkling, there is blackspot; Also can destroy the immunity function of human body, bring out lymphocyte chromosome pathology, accelerate old and feeble, cause pregnant woman to have a deformed child.The ozone safety standard that the World Health Organization works out is the Cmax allowed under working environment for 8 hours is 0.10ppm (4 × 10
-9mol/L).
The main method of current process ozone has: thermal decomposition method, activated carbon method, pre-ozonation method, dilution method, electromagenetic wave radiation decomposition method, liquid absorption process and catalytic decomposition.Front several method exist energy consumption high, produce secondary pollution and the limitation such as treating capacity is little, and catalytic decomposition ozone can make up the deficiency of above method preferably, can meet high de-agglomeration rate, long-term stability, safety, economic dispatch requirement, be more satisfactory ozone treatment method.
CN1259398A discloses a kind of ozone decomposition catalyst and preparation method thereof.Ozone decomposition catalyst take active carbon as carrier, except containing except manganese dioxide, also contains the metal oxide of nickel or copper or cobalt etc., adopts the preparation of dipping-sedimentation.This catalyst is containing MnO
2be 4 ~ 20% (weight), the content of the oxide of nickel or copper or cobalt is 3 ~ 8% (weight), when containing O in gas
3when concentration is 300 ~ 2000ppm, at 15 DEG C, humidification, air speed are 5 × 10
3~ 2 × 10
4h
-1under condition, the service life of this catalyst can reach 500 ~ 2000 hours.
CN101757933A provides a kind of ozone decomposition catalyst, comprising: the metal foam nickel helping active component as catalyst carrier and catalyst; Overlayed on manganese or the ferriferous oxide on described nickel foam surface by impregnation method as main active component.This invention additionally provides a kind of preparation method of ozone decomposition catalyst, comprises step: the active component solution that A, preparation manganese nitrate or nitric acid ferromanganese are formed; B, the nickel foam as carrier is flooded described active component solution; C, the carrier after dipping to be dried, and dry burning at a certain temperature.
CN1785507A discloses a kind of ozone decomposition catalyst and preparation method thereof, relates to catalysis and field of environment protection.It is characterized in that adopting with the oxide of manganese for main active constituent, interpolation alkali metal or alkaline-earth metal are for helping active constituent, and adopt spraying coating process, load is on metal or ceramic honeycomb carrier.Catalyst of the present invention is mainly used in the catalytic decomposition of electric discharge air ozone, also can be used for NO
x, SO
xcatalytic decomposition.
According to the difference of active component, main ozone decomposition catalyst can be divided into containing Mn catalyst, containing catalyst of transition metal oxide, noble metal catalyst three class.But existing catalyst generally exist cost higher, there is strong steam inhibitory action and the high not series of problems of ozone decomposed efficiency.
Therefore, development of new has high ozone degrading activity, adapts to the catalyst system of high ozone concentration, high humility, has very important Significance for Environment.
Summary of the invention
For the deficiencies in the prior art, the life-span existed for the catalyst solving existing catalytic decomposition ozone is short, moisture resistance is poor, use noble metal to cause the problem of high cost, the invention provides a kind of novel manganese base composite oxidate Catalysts and its preparation method, can be used as the catalytic decomposition of the ozone of water or air-treatment and modern industry and household electrical appliance generation.
An object of the present invention is to provide a kind of manganese base composite oxidate catalyst for catalytic decomposition ozone, and described catalyst comprises Mn oxide and at least one transition metal oxide.
In catalyst of the present invention, the mol ratio of manganese element and transition metal is 0.2 ~ 5.0, preferably 2.0 ~ 3.0, further preferably 2.0.
The mixture of a kind of in the preferred titanium of the transition metal in catalyst of the present invention, chromium, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, vanadium, scandium or at least two kinds, such as iron, titanium/chromium, copper/zirconium, molybdenum, the selections such as molybdenum/vanadium/scandium, the mixture of a kind of further preferably in nickel, copper, iron or at least two kinds.
Further, described catalyst is MnO
x-NiO
x, MnO
x-CuO
x, MnO
x-FeO
xdeng bimetal composite oxide catalyst, or MnO
x-NiO
x-CuO
x, MnO
x-NiO
x-FeO
x, MnO
x-CuO
x-FeO
x, MnO
x-NiO
x-CuO
x-FeO
xdeng composite oxide catalysts.
Another object of the present invention is to the preparation method providing a kind of manganese base composite oxidate catalyst, described preparation method is the precipitation method or hydrothermal synthesis method.
The precipitation method of the present invention comprise the steps:
(1) manganese salt and transition metal salt are made into mixed solution;
(2) add precipitating reagent under agitation, precipitation reaction occurs;
(3) Separation of Solid and Liquid, washing are carried out to the mixed system that step (2) obtains, obtain filter cake;
(4) filtration cakes torrefaction step (3) obtained, roasting, namely obtain manganese base composite oxidate catalyst.
Manganese salt described in step of the present invention (1) is soluble manganese salt, the mixture of a kind of in preferred manganese chloride, manganese nitrate, manganese sulfate or at least two kinds, such as manganese chloride, manganese nitrate/manganese sulfate, manganese chloride/manganese nitrate/manganese sulfate, manganese nitrate etc., further preferably sulfuric acid manganese and/or manganese nitrate.
Described transition metal salt is soluble transition metal salt, the mixture of a kind of in preferred mantoquita, nickel salt, molysite or at least two kinds, such as copper nitrate, copper chloride/nickel nitrate, copper chloride/nickel chloride/ferric sulfate, nickel nitrate, copper sulphate/ferric sulfate etc.Described mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, copper sulphate or at least two kinds, such as copper nitrate, copper nitrate/copper chloride, copper nitrate/copper chloride/copper sulphate etc.Nickel salt is preferably the mixture of a kind of in nickel nitrate, nickel chloride, nickelous sulfate or at least two kinds, such as nickelous sulfate, nickel nitrate/nickel chloride, nickel nitrate/nickel chloride/nickelous sulfate etc.Molysite is preferably the mixture of a kind of in ferric nitrate, iron chloride, ferric sulfate or at least two kinds, such as iron chloride, ferric sulfate, ferric nitrate/iron chloride/ferric sulfate etc.Those skilled in the art can be used alone or in combination according to actual needs.
Further, step (2) described precipitating reagent is urea, sodium carbonate, ammoniacal liquor, NaOH, potash, preferred urea, sodium carbonate, ammoniacal liquor;
Preferably, when urea selected by described precipitating reagent, step (2) described mixing time is 4 ~ 48h, preferably 6 ~ 24h, further preferably 9 ~ 15h, most preferably 12h; Preferably, step (2) operating temperature is 60 ~ 100 DEG C, preferably 70 ~ 98 DEG C, preferably 80 ~ 95 DEG C further, most preferably 90 DEG C;
Further, step (3) described Separation of Solid and Liquid is filtration, centrifugation, precipitation, gravitational settling or centrifugal sedimentation; Preferred filtration, centrifugation; Describedly be filtered into suction filtration, press filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration or ultrafiltration.Described filtration is as the criterion with the intrinsic property not changing mixed system.
Further, the described washing of step (3) adopts deionized water washing, washing times preferably 1 ~ 5 time, preferably 2 ~ 4 times further, most preferably 3 times.
Further, step (4) described drying is dried for putting into baking oven.Other drying modes all can be used for the present invention, as natural drying etc.Bake out temperature preferably 80 ~ 120 DEG C, such as 82 DEG C, 90 DEG C, 95 DEG C, 102 DEG C, 110 DEG C, 118 DEG C etc., preferably 90 ~ 112 DEG C further, most preferably 100 DEG C.Drying time is 5 ~ 36h preferably, such as 5h, 8h, 11h, 15h, 20h, 28h, 33h, 35h etc., more preferably 7 ~ 24h, further preferably 9 ~ 12h, most preferably 10h.
Further, step (4) described roasting is carried out in Muffle furnace.Sintering temperature preferably 300 ~ 800 DEG C, such as 320 DEG C, 375 DEG C, 400 DEG C, 420 DEG C, 506 DEG C, 600 DEG C, 700 DEG C, 785 DEG C etc., preferably 380 ~ 650 DEG C further, most preferably 500 DEG C.Roasting time is 3 ~ 24h preferably, such as 4h, 10h, 15h, 18h, 22h etc., further preferably 4 ~ 8h, most preferably 5h.
The reaction pressure of the precipitation method of the present invention is not particularly limited, and usually preferably adopts normal pressure.
Hydrothermal synthesis method of the present invention comprises the steps:
(1) manganese salt and transition metal salt are made into mixed solution, are adjusted to acidity;
(2), after stirring, the mixed solution of step (1) is moved in water heating kettle;
(3) water heating kettle is placed in heater and carries out hydrothermal synthesis reaction;
(4) by the washing of step (3) hydrothermal synthesis reaction products therefrom, dry, roasting, manganese base composite oxidate catalyst is namely obtained.
Have polytetrafluoroethylene bushing in water heating kettle, corrosion resistance is good, and use procedure unharmful substance overflows, decreasing pollution, use safety, after intensification, boosting, can dissolve the sample being difficult under normal conditions dissolve and the sample containing volatile element in quick nondestructive lost territory.
Manganese salt described in step of the present invention (1) is soluble manganese salt, the mixture of a kind of in preferred potassium permanganate, manganese chloride, manganese nitrate, manganese sulfate or at least two kinds, such as potassium permanganate, potassium permanganate/manganese chloride, manganese chloride/manganese nitrate/manganese sulfate, manganese nitrate, any combination such as potassium permanganate/manganese chloride/manganese nitrate/manganese sulfate all can be used for implementing the present invention, further preferred potassium permanganate and manganese nitrate.
Described transition metal salt is soluble transition metal salt, comprises the mixture of a kind of in mantoquita, nickel salt, molysite or at least two kinds, such as copper nitrate, copper chloride/nickel nitrate, copper chloride/nickel chloride/ferric sulfate, nickel nitrate, copper sulphate/ferric sulfate etc.Described mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, copper sulphate or at least two kinds, such as copper nitrate, copper chloride/copper sulphate, copper nitrate/copper chloride/copper sulphate etc.Nickel salt is preferably the mixture of a kind of in nickel nitrate, nickel chloride, nickelous sulfate or at least two kinds, such as nickel chloride, nickelous sulfate, nickel nitrate/nickel chloride/nickelous sulfate etc.Molysite is preferably the mixture of a kind of in ferric nitrate, iron chloride, ferric sulfate or at least two kinds, such as ferric nitrate/ferric sulfate, iron chloride, ferric nitrate/iron chloride/ferric sulfate etc.
Preferably, the acid that adds of solution acid-basicity is regulated to be the mixture of a kind of in nitric acid, sulfuric acid, hydrochloric acid or hydrofluoric acid or at least two kinds, further preferably nitric acid and/or sulfuric acid;
Preferably, the pH value of solution is adjusted to 0 ~ 6, and more preferably 0 ~ 4;
Further, the mixing time described in step (2) is 0.5 ~ 2h, such as 0.6h, 1.1h, 1.5h, 1.8h etc., further preferably 0.8 ~ 1.5h, most preferably 1h.
Further, step (3) described reaction time preferably 6 ~ 60h, such as 7h, 10h, 15h, 22h, 30h, 40h, 45h, 50h, 53h, 58h etc., further preferably 12 ~ 48h, most preferably 24h.Reaction temperature is 80 ~ 200 DEG C, such as 85 DEG C, 92 DEG C, 102 DEG C, 120 DEG C, 150 DEG C, 168 DEG C, 180 DEG C, 195 DEG C etc., preferably 95 ~ 130 DEG C further, most preferably 100 DEG C.
Further, step (4) described drying is dried for putting into baking oven.Other can make the mode of step (3) products therefrom drying all can be used for the present invention, the modes such as such as natural drying.Bake out temperature preferably 80 ~ 120 DEG C, such as 82 DEG C, 90 DEG C, 98 DEG C, 105 DEG C, 118 DEG C etc., preferably 85 ~ 110 DEG C further, most preferably 100 DEG C.Drying time is preferably 5 ~ 36h, such as 5h, 10h, 15h, 20h, 26h, 30h, 35h etc., more preferably 7 ~ 24h, further preferably 9 ~ 12h, most preferably 10h.
Further, step (4) described roasting is carried out at Muffle furnace.Other baking modes that those skilled in the art can be known all can be used for implementing the present invention.Sintering temperature is 300 ~ 800 DEG C, such as 305 DEG C, 380 DEG C, 400 DEG C, 450 DEG C, 520 DEG C, 600 DEG C, 650 DEG C, 715 DEG C, 780 DEG C etc., preferably 320 ~ 500 DEG C further, most preferably 350 DEG C.Roasting time is 2 ~ 24h preferably, such as 2.2h, 3.5h, 5h, 9h, 15h, 18h, 22h, 23.5h etc., further preferably 3 ~ 6h, most preferably 3h.
Present invention also offers a kind of method of catalytic decomposition ozone, described method uses above-mentioned manganese base composite oxidate catalyst.
By described catalyst slurrying back loading on active carbon, metal or ceramic monolith, be prepared into shaping catalyst and use, or use after extruded.
Compared with prior art scheme, the present invention has following beneficial effect:
(1) the present invention is composite oxide catalysts, and it does not need carrier can reach corresponding dispersion and catalytic effect yet.
(2) at room temperature to ozone decomposed, there is high activity, be applicable to the elimination that indoor ozone pollutes.
(3) rear catalyst of high ozone treatment amount still maintains greater activity, and catalyst life is long.
(4) there is good anti humility performance, can be used in the removal of ozone under certain humidity.
(5) adopt nontoxic component, reduce the harm to health and ecological environment.
The present invention is described in more detail below.But following example is only simple and easy example of the present invention, does not represent or limits the scope of the present invention, and interest field of the present invention is as the criterion with claims.
Detailed description of the invention
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1 precipitation method prepare manganese base composite oxidate catalyst
Manganese nitrate and ferric nitrate are distinguished soluble in water, preparation Mn/Fe mol ratio is the solution of 1 and mixes, excess urea is added in this solution, and 12h is stirred continuously under 90 DEG C of conditions, then carry out suction filtration and wash 3 times obtaining filter cake, filter cake is put into baking oven and dry 10h in 100 DEG C, obtain powder catalyst finally by Muffle furnace roasting 5h in 500 DEG C of air.By obtained catalyst compressing tablet, grind, sieve, get 20 ~ 40 orders for subsequent use, be called catalyst A.
Embodiment 2 precipitation method prepare manganese base composite oxidate catalyst
Manganese chloride and copper sulphate are distinguished soluble in water, preparation Mn/Cu mol ratio is the solution of 0.2 and mixes, slowly excess of sodium carbonate is added while stirring in solution, then carry out suction filtration separation and wash obtaining filter cake, filter cake is put into baking oven and dry 5h in 120 DEG C, obtain powder catalyst finally by Muffle furnace roasting 24h in 300 DEG C of air.By obtained catalyst compressing tablet, grind, sieve, get 20 ~ 40 orders for subsequent use.
Embodiment 3 precipitation method prepare manganese base composite oxidate catalyst
Manganese nitrate and copper sulphate, nickel nitrate are distinguished soluble in water, preparation Mn/ (Cu+Ni) mol ratio is the solution of 0.5 and mixes, slowly while stirring in solution, add excess of sodium carbonate, then carry out vacuum filtration and wash 4 times obtaining filter cake, filter cake is put into baking oven and dry 36h in 80 DEG C, obtain powder catalyst finally by Muffle furnace roasting 3h in 800 DEG C of air.By obtained catalyst compressing tablet, grind, sieve, get 20 ~ 40 orders for subsequent use.
Embodiment 4 precipitation method prepare manganese base composite oxidate catalyst
Manganese nitrate, manganese chloride and ferric nitrate is soluble in water respectively, preparation Mn/Fe mol ratio is the solution of 5.0 and mixes, excess urea is added in this solution, and 24h is stirred continuously under 80 DEG C of conditions, then carry out suction filtration and wash 3 times obtaining filter cake, filter cake is put into baking oven and dry 4h in 112 DEG C, obtain powder catalyst finally by Muffle furnace roasting 6h in 380 DEG C of air.By obtained catalyst compressing tablet, grind, sieve, get 20 ~ 40 orders for subsequent use.
Embodiment 5 hydrothermal synthesis method prepares manganese base composite oxidate catalyst
Appropriate liquor potassic permanganate, manganese sulfate solution, iron nitrate solution and nitric acid are mixed, adjust ph is 0, preparation Mn/Fe mol ratio be the solution mix and blend 1h of 3 to homogeneous, transfer in 100mL water heating kettle, be placed in 100 DEG C of baking ovens and react 24h.After centrifuge washing, 100 DEG C of dry 10h in an oven, finally by Muffle furnace in 350 DEG C of roasting 3h.The grinding of obtained catalyst is sieved, gets 20-40 order for subsequent use, be called catalyst B.Other condition is constant, and changing Mn/Fe mol ratio is 2, obtained catalyst C.Other conditions are constant, and changing Mn/Fe mol ratio is 1, obtained catalyst D.
Embodiment 6 hydrothermal synthesis method prepares manganese base composite oxidate catalyst
By appropriate liquor potassic permanganate, manganese chloride solution and copper nitrate solution and nitric acid mixing, adjust ph is 6, preparation Mn/Cu mol ratio be the solution mix and blend 1.5h of 2 to homogeneous, transfer in 100mL water heating kettle, be placed in 130 DEG C of baking ovens and react 60h.After centrifuge washing, 110 DEG C of dry 12h in an oven, finally by Muffle furnace in 500 DEG C of roasting 10h.The grinding of obtained catalyst is sieved, gets 20-40 order for subsequent use.
Embodiment 7 hydrothermal synthesis method prepares manganese base composite oxidate catalyst
Appropriate liquor potassic permanganate, manganese sulfate solution, copper nitrate solution and nitric acid are mixed, adjust ph is 4, preparation Mn/Cu mol ratio be the solution mix and blend 0.5h of 4.5 to homogeneous, transfer in 100mL water heating kettle, be placed in 80 DEG C of baking ovens and react 5h.After centrifuge washing, 120 DEG C of dry 5h in an oven, finally by Muffle furnace in 300 DEG C of roasting 24h.The grinding of obtained catalyst is sieved, gets 20-40 order for subsequent use.
Embodiment 8 hydrothermal synthesis method prepares manganese base composite oxidate catalyst
Appropriate manganese nitrate solution, manganese sulfate solution, nickel nitrate solution and nitric acid are mixed, adjust ph is 3, preparation Mn/Ni mol ratio be the solution mix and blend 2h of 3 to homogeneous, transfer in 100mL water heating kettle, be placed in 200 DEG C of baking ovens and react 6h.After centrifuge washing, 80 DEG C of dry 36h in an oven, finally by Muffle furnace in 800 DEG C of roasting 2h.The grinding of obtained catalyst is sieved, gets 20-40 order for subsequent use.
Comparative example 1
Ozone decomposition catalyst is prepared by method disclosed in CN1259398A:
The active carbon adopting charcoal to make is carrier, take 20g active carbon, be dissolved in 18 ml distilled waters with 6g manganese nitrate and 5g nickel nitrate, this mixing salt solution is immersed in active carbon, stir, to be put in baking oven at 120 DEG C dry 4 hours, then to be taken out, join 18ml and contain 36% (weight) Na
2cO
3the distilled water solution of concentration, immerses in above semi-finished product, at 120 DEG C dry 4 hours, washs 10 times with warm distilled water, then puts into baking oven at 120 DEG C dry 8 hours, namely obtains finished product ozone decomposition catalyst.
Comparative example 2
Ozone decomposition catalyst is prepared by method disclosed in CN1785507A:
Measure 40ml10% industrial nitric acid manganese solution under high shear with 20ml7% liquor potassic permanganate hybrid reaction, continue emulsification 2 hours, obtain solution A.After the aluminium alloy of 210 × 50 × 30mm being adopted traditional pickling, alkali cleaning, the pretreatment of washing stoving process, solution A is sprayed on the good carrier of pretreatment, dry 4 hours for 80 DEG C, repeatedly spray, 15% is reached to carrier rate of body weight gain, 500 DEG C of roastings obtain catalyst in 4 hours, and the thickness of catalyst coat is at 0.01mm.
The embodiment of the present invention 1,5 and comparative example 1,2 are carried out contrast test as follows:
1, catalyst activity is investigated
The ozone decomposition catalyst that ferromanganese composite oxide catalysts B and C obtain ferromanganese composite oxide catalysts A obtained for embodiment 1, embodiment 5 and comparative example 1,2 obtain, the activity that homemade micro fixed-bed reactor carries out catalysis ozone decomposition is investigated.The consumption of catalyst is 0.2g, react normal pressure, 25 DEG C carry out, ozone entrance concentration is 10000ppm, and gas flow is 40mL/min, 90% relative humidity.Ozone Monitor is used to detect halitosis oxygen concentration.
Result shows: catalyst A catalysis ozone decomposes in 2h, and activity is 80%; After catalyst B catalysis ozone decomposes 6h, ozone conversion efficiency is 85%.Catalyst C is after catalysis ozone decomposes 6h, and ozone conversion efficiency is 95%, and catalyst D is after catalysis ozone decomposes 6h, and ozone conversion efficiency is only 75%.From upper result, catalyst C has best catalytic decomposition ozone activity and the ability of resistance to high humility.
And the ozone decomposition catalyst that comparative example 1 obtains is after catalysis ozone decomposes 6h, ozone conversion efficiency is only 42%.Under the same conditions, after catalysis ozone decomposes 6h, ozone conversion efficiency is only 36% to comparative example 2.
2, relative humidity impact is investigated
The ozone decomposition catalyst using catalyst C and comparative example 1,2 to obtain, homemade fixed bed reactors are investigated the impact of different humidity on catalyst activity.The consumption of catalyst is 0.2g, react normal pressure, 25 DEG C carry out, ozone entrance concentration is 10000ppm, and gas flow is 40mL/min.Ozone Monitor is used to detect halitosis oxygen concentration.
Result shows: catalyst C is under relative humidity is the condition of 40%, and after catalysis 6h, catalytic activity still keeps 100%.Even if at catalytic decomposition ozone 66h, process catalytic activity after ozone amount reaches 1560g and still keep 100%, long catalytic life.Under the condition of relative humidity higher than 90%, catalyst C is after catalysis ozone decomposes 6h, and ozone conversion efficiency is still up to 95%.This illustrates that catalyst prepared by the present invention has good moisture resistance, even if when relative humidity is higher, also can reach very high ozone conversion efficiency.
And the ozone decomposition catalyst that comparative example 1 obtains is under relative humidity is 40% condition, after catalysis ozone decomposes 6h, ozone conversion efficiency is 80%.Under relative humidity is 70% condition, after catalysis ozone decomposes 6h, ozone conversion efficiency is only 55%, have dropped 25%.
The ozone decomposition catalyst that comparative example 2 obtains is under relative humidity is 40% condition, and after catalysis ozone decomposes 6h, ozone conversion efficiency is 85%.Under relative humidity is 70% condition, after catalysis ozone decomposes 6h, ozone conversion efficiency is only 48%, have dropped 37%.
This illustrates that steam has stronger inhibitory action to comparative example ozone decomposition catalyst, and high relative humidity can cause comparative example catalytic decomposition of ozone efficiency obviously to decline.
Applicant states, the present invention illustrates preparation process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned preparation process, does not namely mean that the present invention must rely on above-mentioned preparation process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention, all drops within protection scope of the present invention and open scope.
Claims (63)
1. for a manganese base composite oxidate catalyst for catalytic decomposition ozone, it is characterized in that, in described catalyst, the mol ratio of manganese element and transition metal is 0.2 ~ 1;
Described catalyst is MnO
x-NiO
x-CuO
xcomposite oxide catalysts.
2. a preparation method for manganese base composite oxidate catalyst as claimed in claim 1, is characterized in that, described preparation method is the precipitation method, and reaction pressure is normal pressure, and the described precipitation method comprise the steps:
(1) manganese salt and transition metal salt are made into mixed solution;
(2) add precipitating reagent under agitation, precipitation reaction occurs;
(3) Separation of Solid and Liquid, washing are carried out to the mixed system that step (2) obtains, obtain filter cake;
(4) filtration cakes torrefaction step (3) obtained, roasting, namely obtain manganese base composite oxidate catalyst;
Described drying is dried for putting into baking oven, and bake out temperature is 80 ~ 120 DEG C; Drying time is 5 ~ 36h; Described roasting is carried out in Muffle furnace, and sintering temperature is 300 ~ 800 DEG C; Roasting time is 3 ~ 24h.
3. preparation method as claimed in claim 2, it is characterized in that, the manganese salt described in step (1) is soluble manganese salt.
4. preparation method as claimed in claim 3, is characterized in that, described manganese salt is the mixture of a kind of in manganese chloride, manganese nitrate, manganese sulfate or at least two kinds.
5. preparation method as claimed in claim 4, it is characterized in that, described manganese salt is manganese sulfate and/or manganese nitrate.
6. preparation method as claimed in claim 2, it is characterized in that, described transition metal salt is soluble transition metal salt.
7. preparation method as claimed in claim 6, it is characterized in that, described transition metal salt is the mixture of mantoquita, nickel salt.
8. preparation method as claimed in claim 7, is characterized in that, described mantoquita is the mixture of a kind of in copper nitrate, copper chloride, copper sulphate or at least two kinds.
9. preparation method as claimed in claim 7, is characterized in that, described nickel salt is the mixture of a kind of in nickel nitrate, nickel chloride, nickelous sulfate or at least two kinds.
10. preparation method as claimed in claim 2, it is characterized in that, step (2) described precipitating reagent is urea, sodium carbonate, ammoniacal liquor, NaOH, potash.
11. preparation methods as claimed in claim 10, it is characterized in that, described precipitating reagent is urea, sodium carbonate, ammoniacal liquor.
12. preparation methods as claimed in claim 10, is characterized in that, during described precipitating reagent selection urea, step (2) described mixing time is 4 ~ 48h.
13. preparation methods as claimed in claim 12, it is characterized in that, described mixing time is 6 ~ 24h.
14. preparation methods as claimed in claim 13, it is characterized in that, described mixing time is 9 ~ 15h.
15. preparation methods as claimed in claim 14, it is characterized in that, described mixing time is 12h.
16. preparation methods as claimed in claim 2, it is characterized in that, step (2) operating temperature is 60 ~ 100 DEG C.
17. preparation methods as claimed in claim 16, it is characterized in that, step (2) operating temperature is 70 ~ 98 DEG C.
18. preparation methods as claimed in claim 17, it is characterized in that, step (2) operating temperature is 80 ~ 95 DEG C.
19. preparation methods as claimed in claim 18, it is characterized in that, step (2) operating temperature is 90 DEG C.
20. preparation methods as claimed in claim 2, it is characterized in that, step (3) described Separation of Solid and Liquid is filtration, centrifugation, precipitation, gravitational settling or centrifugal sedimentation; Describedly be filtered into suction filtration, press filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration or ultrafiltration.
21. preparation methods as claimed in claim 20, is characterized in that, described Separation of Solid and Liquid is filtration, centrifugation.
22. preparation methods as claimed in claim 2, is characterized in that, the described washing of step (3) adopts deionized water washing.
23. preparation methods as claimed in claim 22, it is characterized in that, described washing times is 1 ~ 5 time.
24. preparation methods as claimed in claim 23, it is characterized in that, described washing times is 2 ~ 4 times.
25. preparation methods as claimed in claim 24, it is characterized in that, described washing times is 3 times.
26. preparation methods as claimed in claim 2, it is characterized in that, step (4) described bake out temperature is 90 ~ 112 DEG C.
27. preparation methods as claimed in claim 26, it is characterized in that, described bake out temperature is 100 DEG C.
28. preparation methods as claimed in claim 2, it is characterized in that, step (4) described drying time is 7 ~ 24h.
29. preparation methods as claimed in claim 28, it is characterized in that, described drying time is 9 ~ 12h.
30. preparation methods as claimed in claim 29, it is characterized in that, described drying time is 10h.
31. preparation methods as claimed in claim 2, it is characterized in that, step (4) described sintering temperature is 380 ~ 650 DEG C.
32. preparation methods as claimed in claim 31, it is characterized in that, described sintering temperature is 500 DEG C.
33. preparation methods as claimed in claim 2, it is characterized in that, step (4) described roasting time is 4 ~ 8h.
34. preparation methods as claimed in claim 33, it is characterized in that, described roasting time is 5h.
The preparation method of 35. 1 kinds of manganese base composite oxidate catalyst as claimed in claim 1, is characterized in that, described preparation method is hydrothermal synthesis method, and described hydrothermal synthesis method comprises the steps:
(1) manganese salt and transition metal salt are made into mixed solution, being adjusted to pH value is 0 ~ 6;
(2), after stirring, the mixed solution of step (1) is moved in water heating kettle;
(3) water heating kettle is placed in heater and carries out hydrothermal synthesis reaction, the reaction time is 6 ~ 60h, and reaction temperature is 80 ~ 200 DEG C;
(4) by the washing of step (3) hydrothermal synthesis reaction products therefrom, dry, roasting, manganese base composite oxidate catalyst is namely obtained; Described drying is dried for putting into baking oven, and bake out temperature is 80 ~ 120 DEG C, and drying time is 5 ~ 36h; Described roasting is carried out at Muffle furnace, and sintering temperature is 300 ~ 800 DEG C, and roasting time is 2 ~ 24h.
36. preparation methods as claimed in claim 35, it is characterized in that, the manganese salt described in step (1) is soluble manganese salt.
37. preparation methods as claimed in claim 36, is characterized in that, described manganese salt is the mixture of a kind of in potassium permanganate, manganese chloride, manganese nitrate, manganese sulfate or at least two kinds.
38. preparation methods as claimed in claim 37, it is characterized in that, described manganese salt is potassium permanganate and manganese nitrate.
39. preparation methods as claimed in claim 35, it is characterized in that, described transition metal salt is soluble transition metal salt.
40. preparation methods as claimed in claim 39, it is characterized in that, described transition metal salt is the mixture of mantoquita, nickel salt.
41. preparation methods as claimed in claim 40, is characterized in that, described mantoquita is the mixture of a kind of in copper nitrate, copper chloride, copper sulphate or at least two kinds.
42. preparation methods as claimed in claim 40, is characterized in that, described nickel salt is the mixture of a kind of in nickel nitrate, nickel chloride, nickelous sulfate or at least two kinds.
43. preparation methods as claimed in claim 35, is characterized in that, the acid that described adjust ph adds is the mixture of a kind of in nitric acid, sulfuric acid, hydrochloric acid or hydrofluoric acid or at least two kinds.
44. preparation methods as claimed in claim 43, it is characterized in that, described acid is nitric acid and/or sulfuric acid.
45. preparation methods as claimed in claim 35, it is characterized in that, the pH value of solution is adjusted to 0 ~ 4.
46. preparation methods as claimed in claim 35, it is characterized in that, the mixing time described in step (2) is 0.5 ~ 2h.
47. preparation methods as claimed in claim 46, it is characterized in that, described mixing time is 0.8 ~ 1.5h.
48. preparation methods as claimed in claim 47, it is characterized in that, described mixing time is 1h.
49. preparation methods as claimed in claim 35, it is characterized in that, step (3) the described reaction time is 12 ~ 48h.
50. preparation methods as claimed in claim 49, it is characterized in that, the described reaction time is 24h.
51. preparation methods as claimed in claim 35, it is characterized in that, step (3) described reaction temperature is 95 ~ 130 DEG C.
52. preparation methods as claimed in claim 51, it is characterized in that, described reaction temperature is 100 DEG C.
53. preparation methods as claimed in claim 35, it is characterized in that, step (4) bake out temperature is 85 ~ 110 DEG C.
54. preparation methods as claimed in claim 53, it is characterized in that, bake out temperature is 100 DEG C.
55. preparation methods as claimed in claim 35, it is characterized in that, step (4) drying time is 7 ~ 24h.
56. preparation methods as claimed in claim 55, it is characterized in that, drying time is 9 ~ 12h.
57. preparation methods as claimed in claim 56, it is characterized in that, drying time is 10h.
58. preparation methods as claimed in claim 35, it is characterized in that, step (4) sintering temperature is 320 ~ 500 DEG C.
59. preparation methods as claimed in claim 58, it is characterized in that, sintering temperature is 350 DEG C.
60. preparation methods as claimed in claim 35, it is characterized in that, step (4) roasting time is 3 ~ 9h.
61. preparation methods as claimed in claim 60, it is characterized in that, roasting time is 3h.
The method of 62. 1 kinds of catalytic decomposition ozone, is characterized in that, described method uses manganese base composite oxidate catalyst as claimed in claim 1.
63. methods as claimed in claim 62, is characterized in that, described catalyst slurrying back loading, on active carbon, metal or ceramic monolith, is prepared into shaping catalyst and uses, or use after extruded.
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