CN102600861A - Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst - Google Patents
Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst Download PDFInfo
- Publication number
- CN102600861A CN102600861A CN2012100829862A CN201210082986A CN102600861A CN 102600861 A CN102600861 A CN 102600861A CN 2012100829862 A CN2012100829862 A CN 2012100829862A CN 201210082986 A CN201210082986 A CN 201210082986A CN 102600861 A CN102600861 A CN 102600861A
- Authority
- CN
- China
- Prior art keywords
- manganese
- catalyst
- preferred
- further preferred
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Abstract
The invention relates to a manganese-based composite oxide catalyst for catalytically decomposing ozone, and a preparation method of the catalyst. The catalyst comprises manganese oxide and at least one transition metal oxide. The preparation method is a homogeneous precipitation method or a hydrothermal synthesis method. The manganese-based composite oxide catalyst adopts innocuous and non-poisonous materials, prepares a manganese-based composite oxide catalyst with high catalytic activity, good wet resistance and high catalytic deposition content by the simple and easy method, so that the catalyst is suitable for catalytically decomposing ozone produced in water or air treatment and modern industry and home 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 that is used for catalytic decomposition ozone, particularly a kind of manganese base composite oxidate Catalysts and its preparation method that is used for catalytic decomposition at the ozone of water or air-treatment and modern industry and household electrical appliance generation.
Background technology
Ozone (O
3) and oxygen (O
2) be the allotrope of oxygen element, under the normal temperature, ozone (O
3) be a kind of unsettled lavender gas that special fishy smell is arranged.In recent years, because its strong oxidizing property, ozone obtains increasingly extensive application as disinfectant, bactericide and deodorant in wastewater treatment.But the residual ozone that has not consumed behind the processing water will be discharged into contaminated environment in the atmosphere.Perfect raising along with modern office equipment; Machines such as volume copying machine, printing machine, facsimile machine, and the use of dust catcher, air cleaner produce ozone through corona discharge; Make the ozone in the surrounding environment accumulate gradually, harmful during excessive concentration.These ozone are not processed direct entering atmosphere, and various life entities and living environment thereof are produced harm.Ozone can the intense stimulus people respiratory tract, cause abscess of throat, cough uncomfortable in chest, cause bronchitis and pulmonary emphysema; Can cause people's neurotoxic, dizziness headache, eyesight descend, are losing one's memory; Can play destruction to the vitamin E in the human body skin, cause people's skin wrinkling, blackspot occurs; Also can destroy the immunity function of human body, bring out lymphocyte chromosome pathology, quicken aging, cause the pregnant woman to have a deformed child.The ozone safety standard that the World Health Organization works out is that the Cmax that allowed under the working environment in 8 hours is 0.10ppm (4 * 10
-9Mol/L).
The main method of handling ozone at present has: thermal decomposition method, activated carbon method, pre-ozonation method, dilution method, electromagenetic wave radiation decomposition method, soup absorption process and catalytic decomposition method.There are limitation such as energy consumption height, generation secondary pollution and treating capacity are little in preceding several method; And catalytic decomposition ozone can remedy the deficiency of above method preferably; Can satisfy 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 is a carrier with the active carbon, except that containing manganese dioxide, also contains the metal oxide of nickel or copper or cobalt etc., adopts the preparation of dipping-sedimentation.This catalyst contains MnO
2Be 4～20% (weight), the content of the oxide of nickel or copper or cobalt is 3～8% (weight), in gas, contains O
3When concentration is 300～2000ppm, be 5 * 10 in 15 ℃ of following humidifications, air speed
3～2 * 10
4h
-1Under the condition, can reach 500～2000 hours the service life of this catalyst.
CN101757933A provides a kind of ozone decomposition catalyst, comprising: the metal foam nickel that helps active component as catalyst carrier and catalyst; Overlay on the manganese or the ferriferous oxide on said nickel foam surface through impregnation method as main active component.This invention also 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 constitute; B, will flood said active component solution as the nickel foam of carrier; C, with soaked carrier oven dry, and baking is burnt 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 the oxide with manganese is main active constituent, add alkali metal or alkaline-earth metal, adopt spraying coating process, load on metal or the ceramic honeycomb carrier for helping active constituent.Catalyst of the present invention is mainly used in the catalytic decomposition of 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 and contain Mn catalyst, contains catalyst of transition metal oxide, three types of noble metal catalysts.But existing catalyst generally exist cost higher, have strong steam inhibitory action and high inadequately a series of problems of ozone decomposition efficiency.
Therefore, development of new has the 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
Deficiency to prior art;, use noble metal poor for life-span weak point, moisture resistance that the catalyst that solves existing catalytic decomposition ozone exists causes expensive problem; 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.
One of the object of the invention is to provide a kind of manganese base composite oxidate catalyst that is used for catalytic decomposition ozone, and said catalyst comprises Mn oxide and at least a transition metal oxide.
The mol ratio of manganese element and transition metal is 0.2～5.0 in the catalyst according to the invention, preferred 2.0～3.0, further preferred 2.0.
The mixture of a kind of in the preferred titanium of the transition metal in the catalyst according to the invention, chromium, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, vanadium, the scandium or at least two kinds; Iron for example; Titanium/chromium, copper/zirconium, molybdenum; Molybdenum/vanadium/selections such as scandium, the mixture of a kind of in further preferred nickel, copper, the iron or at least two kinds.
Further, said 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 provide a kind of manganese base composite oxidate Preparation of catalysts method, said preparation method is the precipitation method or hydrothermal synthesis method.
The precipitation method according to the invention comprise the steps:
(1) manganese salt and transition metal salt are made into mixed solution;
(2) under stirring condition, add precipitating reagent, precipitation reaction takes place;
(3) mixed system that step (2) is obtained carries out Separation of Solid and Liquid, washing, obtains filter cake;
(4) filtration cakes torrefaction, the roasting that step (3) are obtained promptly obtain manganese base composite oxidate catalyst.
The described manganese salt of step of the present invention (1) is soluble manganese salt, the mixture of a kind of in preferred manganese chloride, manganese nitrate, the manganese sulfate or at least two kinds, for example manganese chloride; Manganese nitrate/manganese sulfate; Manganese chloride/manganese nitrate/manganese sulfate, manganese nitrate etc., further preferably sulfuric acid manganese and/or manganese nitrate.
Said transition metal salt is a soluble transition metal salt, the mixture of a kind of in preferred mantoquita, nickel salt, the molysite or at least two kinds, copper nitrate for example, copper chloride/nickel nitrate, copper chloride/nickel chloride/ferric sulfate, nickel nitrate, copper sulphate/ferric sulfate etc.Said mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, the copper sulphate or at least two kinds, copper nitrate for example, 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, the nickelous sulfate or at least two kinds, nickelous sulfate for example, 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, the ferric sulfate or at least two kinds, iron chloride for example, 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, the said precipitating reagent of step (2) is urea, sodium carbonate, ammoniacal liquor, NaOH, potash, preferred urea, sodium carbonate, ammoniacal liquor;
Preferably, when said precipitating reagent was selected urea, the said mixing time of step (2) was 4～48h, preferred 6～24h, further preferred 9～15h, most preferably 12h; Preferably, step (2) operating temperature is 60～100 ℃, preferred 70～98 ℃, and further preferred 80～95 ℃, most preferably 90 ℃;
Further, the said Separation of Solid and Liquid of step (3) is filtration, centrifugation, deposition, gravitational settling or centrifugal sedimentation; Preferred filtration, centrifugation; Saidly be filtered into suction filtration, press filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration or ultrafiltration.Said filtration is as the criterion with the intrinsic property that does not change mixed system.
Further, the deionized water washing is adopted in the said washing of step (3), preferred 1～5 time of washing times, further preferred 2～4 times, most preferably 3 times.
Further, the said drying of step (4) is dried for putting into baking oven.Other drying modes all can be used for the present invention, like air dry etc.Preferred 80～120 ℃ of bake out temperature, for example 82 ℃, 90 ℃, 95 ℃, 102 ℃, 110 ℃, 118 ℃ etc., further preferred 90～112 ℃, most preferably 100 ℃.Preferred 5～the 36h of drying time, 5h for example, 8h, 11h, 15h, 20h, 28h, 33h, 35h etc., more preferably 7～24h, further preferred 9～12h, most preferably 10h.
Further, the said roasting of step (4) is carried out in Muffle furnace.Preferred 300～800 ℃ of sintering temperature, for example 320 ℃, 375 ℃, 400 ℃, 420 ℃, 506 ℃, 600 ℃, 700 ℃, 785 ℃ etc., further preferred 380～650 ℃, most preferably 500 ℃.Preferred 3～the 24h of roasting time, 4h for example, 10h, 15h, 18h, 22h etc., further preferred 4～8h, most preferably 5h.
The reaction pressure of the precipitation method according to the invention is not special to be limited, the preferred usually normal pressure that adopts.
Hydrothermal synthesis method according to the invention comprises the steps:
(1) manganese salt and transition metal salt are made into mixed solution, are adjusted to acidity;
(2) stir after, the mixed solution of step (1) is moved in the water heating kettle;
(3) place heater to carry out hydrothermal synthesis reaction water heating kettle;
(4) with the washing of step (3) hydrothermal synthesis reaction products therefrom, dry, roasting, promptly obtain manganese base composite oxidate catalyst.
Polytetrafluoroethylene bushing is arranged in the water heating kettle, and corrosion resistance is good, and the use unharmful substance overflows, and reduces and pollutes, and is safe in utilization, after heating up, boosting, can be dissolved in the sample that is difficult to the sample that dissolves under the normal condition and contains volatile element in the quick nondestructive lost territory.
The described manganese salt of step of the present invention (1) is soluble manganese salt; The mixture of a kind of in preferred potassium permanganate, manganese chloride, manganese nitrate, the manganese sulfate or at least two kinds, potassium permanganate for example, potassium permanganate/manganese chloride; Manganese chloride/manganese nitrate/manganese sulfate; Manganese nitrate, potassium permanganate/manganese chloride/combination in any such as manganese nitrate/manganese sulfate all can be used for embodiment of the present invention, further preferred potassium permanganate and manganese nitrate.
Said transition metal salt is a soluble transition metal salt, comprises the mixture of a kind of in mantoquita, nickel salt, the molysite or at least two kinds, copper nitrate for example, copper chloride/nickel nitrate, copper chloride/nickel chloride/ferric sulfate, nickel nitrate, copper sulphate/ferric sulfate etc.Said mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, the copper sulphate or at least two kinds, copper nitrate for example, 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, the nickelous sulfate or at least two kinds, nickel chloride for example, nickelous sulfate, nickel nitrate/nickel chloride/nickelous sulfate etc.Molysite is preferably the mixture of a kind of in ferric nitrate, iron chloride, the ferric sulfate or at least two kinds, ferric nitrate/ferric sulfate for example, iron chloride, ferric nitrate/iron chloride/ferric sulfate etc.
Preferably, the acid that the regulator solution Acidity of Aikalinity is added is the mixture of a kind of in nitric acid, sulfuric acid, hydrochloric acid or the hydrofluoric acid or at least two kinds, further preferred nitric acid and/or sulfuric acid;
Preferably, the pH value of solution is adjusted to 0～6, further is preferably 0～4;
Further, the described mixing time of step (2) is 0.5～2h, 0.6h for example, 1.1h, 1.5h, 1.8h etc., further preferred 0.8～1.5h, most preferably 1h.
Further, preferred 6～60h of said reaction time of step (3), 7h for example, 10h, 15h, 22h, 30h, 40h, 45h, 50h, 53h, 58h etc., further preferred 12～48h, most preferably 24h.Reaction temperature is 80～200 ℃, for example 85 ℃, and 92 ℃, 102 ℃, 120 ℃, 150 ℃, 168 ℃, 180 ℃, 195 ℃ etc., further preferred 95～130 ℃, most preferably 100 ℃.
Further, the said drying of step (4) is dried for putting into baking oven.Other can make the dry mode of step (3) products therefrom all can be used for the present invention, for example mode such as air dry.Preferred 80～120 ℃ of bake out temperature, for example 82 ℃, 90 ℃, 98 ℃, 105 ℃, 118 ℃ etc., further preferred 85～110 ℃, most preferably 100 ℃.Drying time is preferably 5～36h, 5h for example, 10h, 15h, 20h, 26h, 30h, 35h etc., more preferably 7～24h, further preferred 9～12h, most preferably 10h.
Further, the said roasting of step (4) is carried out at Muffle furnace.Other roasting modes that those skilled in the art can be known all can be used for embodiment of the present invention.Sintering temperature is 300～800 ℃, for example 305 ℃, and 380 ℃, 400 ℃, 450 ℃, 520 ℃, 600 ℃, 650 ℃, 715 ℃, 780 ℃ etc., further preferred 320～500 ℃, most preferably 350 ℃.Preferred 2～the 24h of roasting time, 2.2h for example, 3.5h, 5h, 9h, 15h, 18h, 22h, 23.5h etc., further preferred 3～6h, most preferably 3h.
The present invention also provides a kind of method of catalytic decomposition ozone, and said method is used above-mentioned manganese base composite oxidate catalyst.
On active carbon, metal or ceramic monolith, the catalyst that is prepared into moulding uses with said catalyst slurrying back loading, or through using after the extrusion modling.
Compare with the prior art scheme, the present invention has following beneficial effect:
(1) the present invention is a composite oxide catalysts, and it does not need carrier can reach corresponding dispersion and catalytic effect yet.
(2) at room temperature decomposition has high activity to ozone, is applicable to the elimination that indoor ozone pollutes.
(3) catalyst is still kept greater activity after the high ozone treatment amount, and catalyst life is long.
(4) have anti humility performance preferably, can be used in the removal of ozone under certain humidity.
(5) adopt nontoxic component, reduce harm health and ecological environment.
Down in the face of further explain of the present invention.But following instance only is a simple and easy example of the present invention, does not represent or limits rights protection scope of the present invention, and interest field of the present invention is as the criterion with claims.
The specific embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1 precipitation method prepare manganese base composite oxidate catalyst
Manganese nitrate and ferric nitrate is soluble in water respectively; Preparation Mn/Fe mol ratio is 1 solution and mixes; In this solution, add excessive urea, and under 90 ℃ of conditions continuous stirring 12h, carry out suction filtration then and wash 3 times obtaining filter cake; Filter cake is put into baking oven in 100 ℃ of oven dry 10h, after Muffle furnace roasting 5h in 500 ℃ of air makes powder catalyst.With the catalyst compressing tablet that makes, grind, sieve, it is subsequent use to get 20～40 orders, is called catalyst A.
Embodiment 2 precipitation method prepare manganese base composite oxidate catalyst
Manganese chloride and copper sulphate is soluble in water respectively; Preparation Mn/Cu mol ratio is 0.2 solution and mixes; In solution, slowly add excess of sodium carbonate while stirring; Carry out suction filtration separation and washing then and obtain filter cake, filter cake is put into baking oven in 120 ℃ of oven dry 5h, after Muffle furnace roasting 24h in 300 ℃ of air makes powder catalyst.With the catalyst compressing tablet that makes, grind, sieve, it is subsequent use to get 20～40 orders.
Embodiment 3 precipitation method prepare manganese base composite oxidate catalyst
Distinguish manganese nitrate and copper sulphate, nickel nitrate soluble in water; Preparation Mn/ (Cu+Ni) mol ratio is 0.5 solution and mixes; Slowly in solution, add excess of sodium carbonate while stirring; Carry out vacuum filtration then and wash 4 times obtaining filter cake, filter cake is put into baking oven in 80 ℃ of oven dry 36h, after Muffle furnace roasting 3h in 800 ℃ of air makes powder catalyst.With the catalyst compressing tablet that makes, grind, sieve, it is subsequent use to get 20～40 orders.
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 5.0 solution and mixes; In this solution, add excessive urea, and under 80 ℃ of conditions continuous stirring 24h, carry out suction filtration then and wash 3 times obtaining filter cake; Filter cake is put into baking oven in 112 ℃ of oven dry 4h, after Muffle furnace roasting 6h in 380 ℃ of air makes powder catalyst.With the catalyst compressing tablet that makes, grind, sieve, it is subsequent use to get 20～40 orders.
Embodiment 5 hydrothermal synthesis methods prepare manganese base composite oxidate catalyst
An amount of liquor potassic permanganate, manganese sulfate solution, iron nitrate solution and nitric acid are mixed, and regulating pH value is 0, and preparation Mn/Fe mol ratio is that 3 solution mixes stirring 1h to homogeneous, transfers in the 100mL water heating kettle, places 100 ℃ of baking ovens to react 24h.Behind the centrifuge washing, 100 ℃ of dry 10h in baking oven, after Muffle furnace in 350 ℃ of roasting 3h.Prepared catalyst grinding is sieved, and it is subsequent use to get the 20-40 order, is called catalyst B.Other condition is constant, and changing the Mn/Fe mol ratio is 2, makes catalyst C.Other conditions are constant, and changing the Mn/Fe mol ratio is 1, makes catalyst D.
Embodiment 6 hydrothermal synthesis methods prepare manganese base composite oxidate catalyst
An amount of liquor potassic permanganate, manganese chloride solution and copper nitrate solution and nitric acid are mixed, and regulating pH value is 6, and preparation Mn/Cu mol ratio is that 2 solution mixes stirring 1.5h to homogeneous, transfers in the 100mL water heating kettle, places 130 ℃ of baking ovens to react 60h.Behind the centrifuge washing, 110 ℃ of dry 12h in baking oven, after Muffle furnace in 500 ℃ of roasting 10h.Prepared catalyst grinding is sieved, and it is subsequent use to get the 20-40 order.
Embodiment 7 hydrothermal synthesis methods prepare manganese base composite oxidate catalyst
An amount of liquor potassic permanganate, manganese sulfate solution, copper nitrate solution and nitric acid are mixed, and regulating pH value is 4, and preparation Mn/Cu mol ratio is that 4.5 solution mixes stirring 0.5h to homogeneous, transfers in the 100mL water heating kettle, places 80 ℃ of baking ovens to react 5h.Behind the centrifuge washing, 120 ℃ of dry 5h in baking oven, after Muffle furnace in 300 ℃ of roasting 24h.Prepared catalyst grinding is sieved, and it is subsequent use to get the 20-40 order.
Embodiment 8 hydrothermal synthesis methods prepare manganese base composite oxidate catalyst
An amount of manganese nitrate solution, manganese sulfate solution, nickel nitrate solution and nitric acid are mixed, and regulating pH value is 3, and preparation Mn/Ni mol ratio is that 3 solution mixes stirring 2h to homogeneous, transfers in the 100mL water heating kettle, places 200 ℃ of baking ovens to react 6h.Behind the centrifuge washing, 80 ℃ of dry 36h in baking oven, after Muffle furnace in 800 ℃ of roasting 2h.Prepared catalyst grinding is sieved, and it is subsequent use to get the 20-40 order.
Comparative Examples 1
Prepare ozone decomposition catalyst by the CN1259398A disclosed method:
The active carbon that adopts charcoal to process is a carrier, takes by weighing the 20g active carbon, is dissolved in 18 ml distilled waters with 6g manganese nitrate and 5g nickel nitrate; This mixing salt solution is immersed in active carbon, stirs, be put in the baking oven 120 ℃ dry 4 hours down; With its taking-up, join 18ml and contain 36% (weight) Na again
2CO
3The distilled water solution of concentration immerses in the above semi-finished product, in 120 ℃ dry 4 hours down, with warm distilled water washing 10 times, put into again baking oven in 120 ℃ dry 8 hours down, promptly obtain the finished product ozone decomposition catalyst.
Comparative Examples 2
Prepare ozone decomposition catalyst by the CN1785507A disclosed method:
Measure 40ml 10% industrial nitric acid manganese solution under high shear with 20ml 7% liquor potassic permanganate hybrid reaction, continued emulsification 2 hours, solution A.After the pickling that the aluminium alloy employing of 210 * 50 * 30mm is traditional, alkali cleaning, the preliminary treatment of washing stoving process; Solution A is sprayed on the good carrier of preliminary treatment; 80 ℃ of oven dry 4 hours, spraying repeatedly reaches 15% to the carrier rate of body weight gain; 500 ℃ of roastings got catalyst in 4 hours, and the thickness of catalyst coat is at 0.01mm.
The embodiment of the invention 1,5 and Comparative Examples 1,2 are compared test as follows:
1, catalyst activity is investigated
The ozone decomposition catalyst that the ferromanganese composite oxide catalysts A that embodiment 1 is made, the ferromanganese composite oxide catalysts B that embodiment 5 makes and C and Comparative Examples 1,2 make carries out the activity that catalysis ozone decomposes and investigates on homemade micro fixed-bed reactor.Catalyst consumption is 0.2g, is reflected at normal pressure, 25 ℃ and carries out, and the ozone entrance concentration is 10000ppm, and gas flow is 40mL/min, 90% relative humidity.Use the ozone detector to detect the halitosis oxygen concentration.
The result shows: the catalyst A catalysis ozone decomposes in the 2h, and activity is 80%; After the catalyst B catalysis ozone decomposed 6h, the ozone transformation efficiency was 85%.Catalyst C is after catalysis ozone decomposes 6h, and the ozone transformation efficiency is 95%, and catalyst D is after catalysis ozone decomposes 6h, and the ozone transformation efficiency is merely 75%.Visible by last result, catalyst C has the best catalytic decomposition ozone activity and the ability of anti-high humility.
And the ozone decomposition catalyst that Comparative Examples 1 makes is after catalysis ozone decomposes 6h, and the ozone transformation efficiency is merely 42%.Comparative Examples 2 under the same conditions, after catalysis ozone decomposed 6h, the ozone transformation efficiency was merely 36%.
2, the relative humidity influence is investigated
The ozone decomposition catalyst that uses catalyst C and Comparative Examples 1,2 to make is investigated the influence of different humidity to catalyst activity on homemade fixed bed reactors.Catalyst consumption is 0.2g, is reflected at normal pressure, 25 ℃ and carries out, and the ozone entrance concentration is 10000ppm, and gas flow is 40mL/min.Use the ozone detector to detect the halitosis oxygen concentration.
The result shows: catalyst C is that behind the catalysis 6h, catalytic activity still keeps 100% under 40% the condition in relative humidity.Even at catalytic decomposition ozone 66h, catalytic activity still kept 100%, long catalytic life after the processing ozone amount reached 1560g.Be higher than in relative humidity under 90% the condition, catalyst C is after catalysis ozone decomposes 6h, and the ozone transformation efficiency is still up to 95%.Catalyst of this explanation the present invention preparation has moisture resistance preferably, even when relative humidity is higher, also can reach very high ozone transformation efficiency.
And the ozone decomposition catalyst that Comparative Examples 1 makes is under 40% condition in relative humidity, and after catalysis ozone decomposed 6h, the ozone transformation efficiency was 80%.In relative humidity is under 70% condition, and after catalysis ozone decomposed 6h, the ozone transformation efficiency was merely 55%, has descended 25%.
The ozone decomposition catalyst that Comparative Examples 2 makes is under 40% condition in relative humidity, and after catalysis ozone decomposed 6h, the ozone transformation efficiency was 85%.In relative humidity is under 70% condition, and after catalysis ozone decomposed 6h, the ozone transformation efficiency was merely 48%, has descended 37%.
This explanation steam has stronger inhibitory action to the Comparative Examples ozone decomposition catalyst, and high relative humidity can cause Comparative Examples ozone catalytic decomposition efficiency obviously to descend.
Applicant's statement, the present invention explains preparation process of the present invention through the foregoing description, but the present invention is not limited to above-mentioned preparation process, does not mean that promptly the present invention must rely on above-mentioned preparation process and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of raw material that the present invention selects for use and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a manganese base composite oxidate catalyst that is used for catalytic decomposition ozone is characterized in that said catalyst comprises Mn oxide and at least a transition metal oxide.
2. catalyst as claimed in claim 1 is characterized in that, the mol ratio of manganese element and transition metal is 0.2～5.0 in the said catalyst, preferred 2.0～3.0, further preferred 2.0.
3. according to claim 1 or claim 2 catalyst is characterized in that, the mixture of a kind of in the preferred titanium of the transition metal in the said catalyst, chromium, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, vanadium, the scandium or at least two kinds; The mixture of a kind of in further preferred nickel, copper, the iron or at least two kinds;
Preferably, said catalyst is MnO
x-NiO
x, MnO
x-CuO
x, MnO
x-FeO
xBimetal 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
xComposite oxide catalysts.
4. one kind like the described manganese base composite oxidate of one of claim 1-3 Preparation of catalysts method, it is characterized in that said preparation method is the precipitation method or hydrothermal synthesis method.
5. preparation method as claimed in claim 4 is characterized in that the said precipitation method comprise the steps:
(1) manganese salt and transition metal salt are made into mixed solution;
(2) under stirring condition, add precipitating reagent, precipitation reaction takes place;
(3) mixed system that step (2) is obtained carries out Separation of Solid and Liquid, washing, obtains filter cake;
(4) filtration cakes torrefaction, the roasting that step (3) are obtained promptly obtain manganese base composite oxidate catalyst.
6. preparation method as claimed in claim 5 is characterized in that, the described manganese salt of step (1) is soluble manganese salt, the mixture of a kind of in preferred manganese chloride, manganese nitrate, the manganese sulfate or at least two kinds, further preferably sulfuric acid manganese and/or manganese nitrate;
Preferably, said transition metal salt is a soluble transition metal salt, the mixture of a kind of in preferred mantoquita, nickel salt, the molysite or at least two kinds; Said mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, the copper sulphate or at least two kinds; Nickel salt is preferably the mixture of a kind of in nickel nitrate, nickel chloride, the nickelous sulfate or at least two kinds; Molysite is preferably the mixture of a kind of in ferric nitrate, iron chloride, the ferric sulfate or at least two kinds;
Preferably, the said precipitating reagent of step (2) is urea, sodium carbonate, ammoniacal liquor, NaOH, potash, preferred urea, sodium carbonate, ammoniacal liquor;
Preferably, when said precipitating reagent was selected urea, the said mixing time of step (2) was 4～48h, preferred 6～24h, further preferred 9～15h, most preferably 12h; Preferably, step (2) operating temperature is 60～100 ℃, preferred 70～98 ℃, and further preferred 80～95 ℃, most preferably 90 ℃;
Preferably, the said Separation of Solid and Liquid of step (3) is filtration, centrifugation, deposition, gravitational settling or centrifugal sedimentation; Preferred filtration, centrifugation; Saidly be filtered into suction filtration, press filtration, vacuum filtration, centrifugal filtration, vacuum filtration, membrane filtration or ultrafiltration;
Preferably, the deionized water washing is adopted in the said washing of step (3), preferred 1～5 time of washing times, further preferred 2～4 times, most preferably 3 times;
Preferably, the said drying of step (4) is dried for putting into baking oven; Preferred 80～120 ℃ of bake out temperature, further preferred 90～112 ℃, most preferably 100 ℃; Drying time is preferably 5～36h, more preferably 7～24h, further preferred 9～12h, most preferably 10h;
Preferably, the said roasting of step (4) is carried out in Muffle furnace; Preferred 300～800 ℃ of sintering temperature, further preferred 380～650 ℃, most preferably 500 ℃; Preferred 3～the 24h of roasting time, further preferred 4～8h, most preferably 5h;
Preferably, the reaction pressure of the said precipitation method is a normal pressure.
7. preparation method as claimed in claim 4 is characterized in that said hydrothermal synthesis method comprises the steps:
(1) manganese salt and transition metal salt are made into mixed solution, are adjusted to acidity;
(2) stir after, the mixed solution of step (1) is moved in the water heating kettle;
(3) place heater to carry out hydrothermal synthesis reaction water heating kettle;
(4) with the washing of step (3) hydrothermal synthesis reaction products therefrom, dry, roasting, promptly obtain manganese base composite oxidate catalyst.
8. preparation method as claimed in claim 7; It is characterized in that; The described manganese salt of step (1) is soluble manganese salt, the mixture of a kind of in preferred potassium permanganate, manganese chloride, manganese nitrate, the manganese sulfate or at least two kinds, further preferred potassium permanganate and manganese nitrate;
Preferably, said transition metal salt is a soluble transition metal salt, the mixture of a kind of in preferred mantoquita, nickel salt, the molysite or at least two kinds; Said mantoquita is preferably the mixture of a kind of in copper nitrate, copper chloride, the copper sulphate or at least two kinds; Nickel salt is preferably the mixture of a kind of in nickel nitrate, nickel chloride, the nickelous sulfate or at least two kinds; Molysite is preferably the mixture of a kind of in ferric nitrate, iron chloride, the ferric sulfate or at least two kinds;
Preferably, the acid that said adjusting pH value adds is the mixture of a kind of in nitric acid, sulfuric acid, hydrochloric acid or the 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, further is preferably 0～4;
Preferably, the described mixing time of step (2) is 0.5～2h, further preferred 0.8～1.5h, most preferably 1h;
Preferably, preferred 6～60h of said reaction time of step (3), further preferred 12～48h, most preferably 24h; Reaction temperature is 80～200 ℃, further preferred 95～130 ℃, and most preferably 100 ℃;
Preferably, the said drying of step (4) is dried for putting into baking oven; Preferred 80～120 ℃ of bake out temperature, further preferred 85～110 ℃, most preferably 100 ℃; Drying time is preferably 5～36h, more preferably 7～24h, further preferred 9～12h, most preferably 10h;
Preferably, the said roasting of step (4) is carried out at Muffle furnace; Sintering temperature is 300～800 ℃, further preferred 320～500 ℃, and most preferably 350 ℃; Preferred 2～the 24h of roasting time, further preferred 3～9h, most preferably 3h.
9. the method for a catalytic decomposition ozone is characterized in that, said method is used like the described manganese base composite oxidate of one of claim 1-3 catalyst.
10. method as claimed in claim 9 is characterized in that, said catalyst slurrying back loading is on active carbon, metal or ceramic monolith, and the catalyst that is prepared into moulding uses, or through using after the extrusion modling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210082986.2A CN102600861B (en) | 2012-03-26 | 2012-03-26 | For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210082986.2A CN102600861B (en) | 2012-03-26 | 2012-03-26 | For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102600861A true CN102600861A (en) | 2012-07-25 |
| CN102600861B CN102600861B (en) | 2016-03-16 |
Family
ID=46518848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210082986.2A Active CN102600861B (en) | 2012-03-26 | 2012-03-26 | For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102600861B (en) |
Cited By (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764589A (en) * | 2012-08-03 | 2012-11-07 | 北京化工大学常州先进材料研究院 | Ozone-containing waste gas treatment device |
| CN103288202A (en) * | 2013-06-27 | 2013-09-11 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103433054A (en) * | 2013-08-13 | 2013-12-11 | 桐乡市健民过滤材料有限公司 | Compound catalyst for removing formaldehyde and preparation method of compound catalyst |
| CN103447026A (en) * | 2013-07-02 | 2013-12-18 | 天津大学 | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof |
| CN103816918A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Weak-crystallization nanometer manganese oxide base adsorbing/catalyzing agent and preparation method thereof |
| CN104001502A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院生态环境研究中心 | Cerium-manganese catalyst for decomposing ozone at room temperature in high humidity as well as preparation method and application of cerium-manganese catalyst |
| CN104014360A (en) * | 2014-06-12 | 2014-09-03 | 东南大学 | Multi-metal oxygen-group catalyst for unsymmetrical dimethylhydrazine degradation and preparation method and application thereof |
| CN104190433A (en) * | 2014-08-15 | 2014-12-10 | 浙江省环境保护科学设计研究院 | Catalytic ozonation catalyst for volatile organic waste gas treatment as well as preparation method and application of catalytic ozonation catalyst |
| CN104258873A (en) * | 2014-09-25 | 2015-01-07 | 江苏省环境科学研究院 | Preparation method for composite ozone catalysis and oxidation catalyst |
| CN104353355A (en) * | 2014-11-14 | 2015-02-18 | 上海应用技术学院 | Ceramic purifier for purifying ozone in air and preparation method of ceramic purifier |
| CN104383940A (en) * | 2014-11-14 | 2015-03-04 | 上海应用技术学院 | Mn3O4/CuO/Ag ternary composite catalyst and preparation method thereof |
| CN104624198A (en) * | 2015-01-28 | 2015-05-20 | 博天环境集团股份有限公司 | Preparation method of catalyst for ozone oxidization |
| CN105540819A (en) * | 2016-01-29 | 2016-05-04 | 中国矿业大学 | Method for treating organic wastewater difficult to degrade by preparing ozone catalyst through modifying carrier |
| CN105536527A (en) * | 2015-12-30 | 2016-05-04 | 芜湖美智空调设备有限公司 | Gas purifying device and preparing method thereof |
| CN105562108A (en) * | 2016-01-19 | 2016-05-11 | 宁波钛安新材料科技有限公司 | Hydrophobic air purifying composite catalyst and preparing method thereof |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN105800735A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Novel manganese-cobalt complex oxide nanoparticle modified ceramic membrane, and assembly and application method thereof in water treatment |
| CN106110763A (en) * | 2016-06-17 | 2016-11-16 | 杭州钛合智造电器有限公司 | A kind of air purifying filter mesh and preparation method thereof |
| CN106179396A (en) * | 2016-07-08 | 2016-12-07 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst of ozone decomposition and preparation method thereof |
| CN106311270A (en) * | 2016-08-17 | 2017-01-11 | 中蓝连海设计研究院 | Preparation method of ozone oxidation catalyst |
| CN106391068A (en) * | 2016-10-19 | 2017-02-15 | 常州大学 | Preparation method of manganese oxide/yttrium phosphate composite catalyst |
| CN106423191A (en) * | 2016-08-30 | 2017-02-22 | 宁波钛安新材料科技有限公司 | Health-care air-purifying composite catalyst material and preparation method thereof |
| CN106622212A (en) * | 2016-12-08 | 2017-05-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Manganese-based catalyst for volatile organic compound governance, and preparation and application thereof |
| CN107486206A (en) * | 2017-09-27 | 2017-12-19 | 中国科学院生态环境研究中心 | A kind of Mn-based material and its production and use |
| CN107519861A (en) * | 2017-08-10 | 2017-12-29 | 中国科学院生态环境研究中心 | A kind of cerium manganese composite oxides catalyst, preparation method and the usage |
| CN107970947A (en) * | 2017-11-30 | 2018-05-01 | 宁波智通环保科技有限公司 | The catalyst and its manufacture method of a kind of ozone decomposition |
| CN108043218A (en) * | 2017-12-12 | 2018-05-18 | 常州大学 | A kind of oxidation of formaldehyde absorber |
| CN108404906A (en) * | 2018-04-17 | 2018-08-17 | 常州大学 | A kind of nano bar-shape manganese chromium composite oxides low-temperature denitration catalyst and preparation method |
| CN108686650A (en) * | 2018-05-16 | 2018-10-23 | 中国科学院城市环境研究所 | A kind of cryptomelane type manganese dioxide, preparation method and use |
| CN108745344A (en) * | 2018-05-31 | 2018-11-06 | 佛山中科鸿翔空气净化技术有限公司 | A kind of preparation method of manganese dioxide-catalyst |
| CN109012735A (en) * | 2018-08-14 | 2018-12-18 | 宁波智通环保科技有限公司 | One kind is except ozone metal oxide catalyst and preparation method thereof |
| CN109046377A (en) * | 2018-09-24 | 2018-12-21 | 上海孚沁环保科技有限公司 | A kind of heterogeneous catalysis and its preparation method and application being catalyzed hydrogen peroxide |
| CN109126771A (en) * | 2018-08-31 | 2019-01-04 | 西南交通大学 | Base metal VOCs catalyst and preparation method thereof |
| CN109224874A (en) * | 2018-11-05 | 2019-01-18 | 南京工业大学 | A kind of catalytic membrane and preparation method thereof for air cleaning |
| CN109261164A (en) * | 2018-10-09 | 2019-01-25 | 广东环境保护工程职业学院 | A kind of copper, the preparation of cobalt codope manganese-based catalyst and its application in low concentration ozone decomposition |
| CN109289863A (en) * | 2018-09-21 | 2019-02-01 | 广东科之源环保科技设备有限公司 | The preparation and its application in low concentration ozone decomposition of a kind of efficiently water-fast Copper-cladding Aluminum Bar manganese-based catalyst |
| CN109550503A (en) * | 2018-11-01 | 2019-04-02 | 中再生乡村环境服务(武汉)有限公司 | A kind of catalyst and preparation method thereof applied to multiple catalyzing ozone oxidation system |
| CN109569643A (en) * | 2018-12-18 | 2019-04-05 | 宁波智通环保科技有限公司 | A kind of support type room temperature removes the preparation method of ozone catalyst |
| CN109772159A (en) * | 2019-03-14 | 2019-05-21 | 中山大学 | A kind of amorphous state manganese oxide catalyst and its preparation method and application |
| CN110227484A (en) * | 2019-07-16 | 2019-09-13 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110252331A (en) * | 2019-06-20 | 2019-09-20 | 宁波智通环保科技有限公司 | A kind of room temperature is except ozone catalyst and preparation method thereof |
| CN110560144A (en) * | 2019-09-25 | 2019-12-13 | 西南石油大学 | Preparation method and application of moisture-proof ozone removal catalyst |
| CN110639542A (en) * | 2019-09-06 | 2020-01-03 | 华南理工大学 | In-situ hybridization room-temperature formaldehyde removal catalyst, composite gel, and preparation method and application thereof |
| CN110652996A (en) * | 2019-10-22 | 2020-01-07 | 天津大学 | Preparation and application of manganese-containing oxide supported molecular sieve catalyst |
| CN110665539A (en) * | 2019-09-25 | 2020-01-10 | 西南石油大学 | Formula and process of manganese silicate-based ozone removal material |
| CN110680170A (en) * | 2019-09-24 | 2020-01-14 | 华南理工大学 | Screen window or curtain capable of removing formaldehyde and VOCs and preparation method thereof |
| CN111495363A (en) * | 2019-01-30 | 2020-08-07 | 宁波方太厨具有限公司 | Preparation method of nanofiber composite filtering membrane for decomposing ozone |
| CN112569928A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone-formaldehyde-benzene co-catalytic degradation catalyst and preparation method and application thereof |
| CN112604693A (en) * | 2020-12-15 | 2021-04-06 | 南京工业大学 | Mesoporous manganese-based composite oxide and preparation method and application thereof |
| CN112808278A (en) * | 2021-01-07 | 2021-05-18 | 浙江工业大学 | Mixed metal nano-magnetic ozone catalyst for degrading antibiotic wastewater and application |
| CN113413896A (en) * | 2021-07-13 | 2021-09-21 | 西南石油大学 | Ozone decomposition catalyst with natural pyrolusite as carrier and preparation method thereof |
| CN113546641A (en) * | 2021-07-26 | 2021-10-26 | 安徽科浦环保科技有限公司 | Preparation method of composite catalytic material for eliminating ozone |
| CN113877602A (en) * | 2021-11-15 | 2022-01-04 | 青岛华世洁环保科技有限公司 | Household deodorizing material for old people and preparation method thereof |
| CN114618589A (en) * | 2020-12-14 | 2022-06-14 | 大连海事大学 | Preparation method and application of ozone degradation catalyst based on iron-based organic framework |
| CN114618475A (en) * | 2022-04-06 | 2022-06-14 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN114700082A (en) * | 2022-04-28 | 2022-07-05 | 江苏蓝溪环境科技有限公司 | Preparation method of catalyst for ozone tail gas destruction |
| CN114832810A (en) * | 2022-05-13 | 2022-08-02 | 福州大学 | Amorphous Zr MnO x Preparation method and advanced oxidation application thereof |
| CN115121258A (en) * | 2022-07-28 | 2022-09-30 | 无锡威孚环保催化剂有限公司 | Ozone eliminating catalyst and preparation method thereof |
| CN115487823A (en) * | 2022-10-19 | 2022-12-20 | 西南石油大学 | Preparation method and application of high-humidity-resistance ozonolysis catalyst |
| CN116273027A (en) * | 2023-05-19 | 2023-06-23 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Sulfur-resistant flue gas ozone decomposition catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380543A (en) * | 2008-09-11 | 2009-03-11 | 南京工业大学 | Fume denitration composite catalyst using titanium-base ceramics as carrier and preparation method thereof |
| US20110079145A1 (en) * | 2009-10-06 | 2011-04-07 | William Dolan | Lower Reactivity Adsorbent and Higher Oxygenate Capacity for Removal of Oxygenates from Olefin Streams |
-
2012
- 2012-03-26 CN CN201210082986.2A patent/CN102600861B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380543A (en) * | 2008-09-11 | 2009-03-11 | 南京工业大学 | Fume denitration composite catalyst using titanium-base ceramics as carrier and preparation method thereof |
| US20110079145A1 (en) * | 2009-10-06 | 2011-04-07 | William Dolan | Lower Reactivity Adsorbent and Higher Oxygenate Capacity for Removal of Oxygenates from Olefin Streams |
Non-Patent Citations (2)
| Title |
|---|
| 刘长安等: "用于臭氧尾气处理的催化剂的制备与表征", 《哈尔滨师范大学自然科学学报》 * |
| 蒋爱丽: "金属氧化物催化臭氧分解规律的研究", 《上海大学硕士学位论文》 * |
Cited By (86)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764589B (en) * | 2012-08-03 | 2014-06-25 | 北京化工大学常州先进材料研究院 | Ozone-containing waste gas treatment device |
| CN102764589A (en) * | 2012-08-03 | 2012-11-07 | 北京化工大学常州先进材料研究院 | Ozone-containing waste gas treatment device |
| CN103288202A (en) * | 2013-06-27 | 2013-09-11 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103288202B (en) * | 2013-06-27 | 2015-04-22 | 江南大学 | Ozonization water treatment method taking iron-nickel magnetic composite material as catalyst |
| CN103447026A (en) * | 2013-07-02 | 2013-12-18 | 天津大学 | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof |
| CN103447026B (en) * | 2013-07-02 | 2014-12-17 | 天津大学 | Wet type catalyzed oxidation manganese-based catalyst and preparation method thereof |
| CN103433054B (en) * | 2013-08-13 | 2016-01-20 | 桐乡市健民过滤材料有限公司 | A kind of except formaldehyde composite catalyst and preparation method thereof |
| CN103433054A (en) * | 2013-08-13 | 2013-12-11 | 桐乡市健民过滤材料有限公司 | Compound catalyst for removing formaldehyde and preparation method of compound catalyst |
| CN103816918A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Weak-crystallization nanometer manganese oxide base adsorbing/catalyzing agent and preparation method thereof |
| CN103816918B (en) * | 2014-03-21 | 2015-11-18 | 中国科学院上海硅酸盐研究所 | Manganese oxide based absorption/the Catalysts and its preparation method of a kind of weak crystallized nano |
| CN104001502A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院生态环境研究中心 | Cerium-manganese catalyst for decomposing ozone at room temperature in high humidity as well as preparation method and application of cerium-manganese catalyst |
| CN104001502B (en) * | 2014-05-29 | 2016-03-16 | 中国科学院生态环境研究中心 | Cerium Mn catalyst, the preparation method and its usage of ozone decomposition under a kind of room temperature high humility |
| CN104014360B (en) * | 2014-06-12 | 2016-08-03 | 东南大学 | Multi-metal oxygen race catalyst for uns-dimethylhydrazine degraded and preparation method and application |
| CN104014360A (en) * | 2014-06-12 | 2014-09-03 | 东南大学 | Multi-metal oxygen-group catalyst for unsymmetrical dimethylhydrazine degradation and preparation method and application thereof |
| CN104190433A (en) * | 2014-08-15 | 2014-12-10 | 浙江省环境保护科学设计研究院 | Catalytic ozonation catalyst for volatile organic waste gas treatment as well as preparation method and application of catalytic ozonation catalyst |
| CN104258873A (en) * | 2014-09-25 | 2015-01-07 | 江苏省环境科学研究院 | Preparation method for composite ozone catalysis and oxidation catalyst |
| CN104383940A (en) * | 2014-11-14 | 2015-03-04 | 上海应用技术学院 | Mn3O4/CuO/Ag ternary composite catalyst and preparation method thereof |
| CN104353355A (en) * | 2014-11-14 | 2015-02-18 | 上海应用技术学院 | Ceramic purifier for purifying ozone in air and preparation method of ceramic purifier |
| CN104624198A (en) * | 2015-01-28 | 2015-05-20 | 博天环境集团股份有限公司 | Preparation method of catalyst for ozone oxidization |
| CN105800767A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Nanometer copper manganate spinel catalytic membrane reactor, and construction and application method thereof in water treatment. |
| CN105800735A (en) * | 2015-10-14 | 2016-07-27 | 北京林业大学 | Novel manganese-cobalt complex oxide nanoparticle modified ceramic membrane, and assembly and application method thereof in water treatment |
| CN105800767B (en) * | 2015-10-14 | 2018-11-09 | 北京林业大学 | The structure of a kind of nanometer of mangaic acid copper spinelle catalytic film reactor and its application process in water process |
| CN105536527A (en) * | 2015-12-30 | 2016-05-04 | 芜湖美智空调设备有限公司 | Gas purifying device and preparing method thereof |
| CN105562108A (en) * | 2016-01-19 | 2016-05-11 | 宁波钛安新材料科技有限公司 | Hydrophobic air purifying composite catalyst and preparing method thereof |
| CN105562108B (en) * | 2016-01-19 | 2018-02-02 | 宁波钛安新材料科技有限公司 | A kind of hydrophobic type purification of air composite catalyst and preparation method thereof |
| CN105540819A (en) * | 2016-01-29 | 2016-05-04 | 中国矿业大学 | Method for treating organic wastewater difficult to degrade by preparing ozone catalyst through modifying carrier |
| CN105540819B (en) * | 2016-01-29 | 2019-02-19 | 中国矿业大学 | A kind of method of support modification preparation ozone catalyst processing organic wastewater with difficult degradation thereby |
| CN106110763A (en) * | 2016-06-17 | 2016-11-16 | 杭州钛合智造电器有限公司 | A kind of air purifying filter mesh and preparation method thereof |
| CN106110763B (en) * | 2016-06-17 | 2019-01-08 | 友好净控科技（浙江）有限公司 | A kind of air purifying filter mesh and preparation method thereof |
| CN106179396B (en) * | 2016-07-08 | 2019-02-15 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst of ozone decomposition and preparation method thereof |
| CN106179396A (en) * | 2016-07-08 | 2016-12-07 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst of ozone decomposition and preparation method thereof |
| CN106311270A (en) * | 2016-08-17 | 2017-01-11 | 中蓝连海设计研究院 | Preparation method of ozone oxidation catalyst |
| CN106311270B (en) * | 2016-08-17 | 2018-09-11 | 中蓝连海设计研究院有限公司 | A kind of preparation method of ozone oxidation catalyst |
| CN106423191A (en) * | 2016-08-30 | 2017-02-22 | 宁波钛安新材料科技有限公司 | Health-care air-purifying composite catalyst material and preparation method thereof |
| CN106391068A (en) * | 2016-10-19 | 2017-02-15 | 常州大学 | Preparation method of manganese oxide/yttrium phosphate composite catalyst |
| CN106391068B (en) * | 2016-10-19 | 2018-10-16 | 常州大学 | A kind of preparation method of manganese oxide/yttrium phosphate composite catalyst |
| CN106622212A (en) * | 2016-12-08 | 2017-05-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Manganese-based catalyst for volatile organic compound governance, and preparation and application thereof |
| CN107519861A (en) * | 2017-08-10 | 2017-12-29 | 中国科学院生态环境研究中心 | A kind of cerium manganese composite oxides catalyst, preparation method and the usage |
| CN107486206A (en) * | 2017-09-27 | 2017-12-19 | 中国科学院生态环境研究中心 | A kind of Mn-based material and its production and use |
| CN107486206B (en) * | 2017-09-27 | 2021-04-02 | 中国科学院生态环境研究中心 | Manganese-based material and preparation method and application thereof |
| CN107970947A (en) * | 2017-11-30 | 2018-05-01 | 宁波智通环保科技有限公司 | The catalyst and its manufacture method of a kind of ozone decomposition |
| CN108043218A (en) * | 2017-12-12 | 2018-05-18 | 常州大学 | A kind of oxidation of formaldehyde absorber |
| CN108404906A (en) * | 2018-04-17 | 2018-08-17 | 常州大学 | A kind of nano bar-shape manganese chromium composite oxides low-temperature denitration catalyst and preparation method |
| CN108404906B (en) * | 2018-04-17 | 2020-12-25 | 常州大学 | Nano-rod-shaped manganese-chromium composite oxide low-temperature denitration catalyst and preparation method thereof |
| CN108686650B (en) * | 2018-05-16 | 2021-09-07 | 中国科学院城市环境研究所 | Cryptomelane type manganese dioxide, preparation method and application thereof |
| CN108686650A (en) * | 2018-05-16 | 2018-10-23 | 中国科学院城市环境研究所 | A kind of cryptomelane type manganese dioxide, preparation method and use |
| CN108745344A (en) * | 2018-05-31 | 2018-11-06 | 佛山中科鸿翔空气净化技术有限公司 | A kind of preparation method of manganese dioxide-catalyst |
| CN109012735A (en) * | 2018-08-14 | 2018-12-18 | 宁波智通环保科技有限公司 | One kind is except ozone metal oxide catalyst and preparation method thereof |
| CN109126771A (en) * | 2018-08-31 | 2019-01-04 | 西南交通大学 | Base metal VOCs catalyst and preparation method thereof |
| CN109126771B (en) * | 2018-08-31 | 2021-09-14 | 西南交通大学 | Non-noble metal VOCs catalyst and preparation method thereof |
| CN109289863A (en) * | 2018-09-21 | 2019-02-01 | 广东科之源环保科技设备有限公司 | The preparation and its application in low concentration ozone decomposition of a kind of efficiently water-fast Copper-cladding Aluminum Bar manganese-based catalyst |
| CN109046377A (en) * | 2018-09-24 | 2018-12-21 | 上海孚沁环保科技有限公司 | A kind of heterogeneous catalysis and its preparation method and application being catalyzed hydrogen peroxide |
| CN109261164A (en) * | 2018-10-09 | 2019-01-25 | 广东环境保护工程职业学院 | A kind of copper, the preparation of cobalt codope manganese-based catalyst and its application in low concentration ozone decomposition |
| CN109550503A (en) * | 2018-11-01 | 2019-04-02 | 中再生乡村环境服务(武汉)有限公司 | A kind of catalyst and preparation method thereof applied to multiple catalyzing ozone oxidation system |
| CN109224874A (en) * | 2018-11-05 | 2019-01-18 | 南京工业大学 | A kind of catalytic membrane and preparation method thereof for air cleaning |
| CN109569643A (en) * | 2018-12-18 | 2019-04-05 | 宁波智通环保科技有限公司 | A kind of support type room temperature removes the preparation method of ozone catalyst |
| CN111495363A (en) * | 2019-01-30 | 2020-08-07 | 宁波方太厨具有限公司 | Preparation method of nanofiber composite filtering membrane for decomposing ozone |
| CN109772159A (en) * | 2019-03-14 | 2019-05-21 | 中山大学 | A kind of amorphous state manganese oxide catalyst and its preparation method and application |
| CN110252331A (en) * | 2019-06-20 | 2019-09-20 | 宁波智通环保科技有限公司 | A kind of room temperature is except ozone catalyst and preparation method thereof |
| CN110227484B (en) * | 2019-07-16 | 2023-11-28 | 河北工业大学 | Doped nano manganese dioxide composite material, preparation method and application thereof |
| CN110227484A (en) * | 2019-07-16 | 2019-09-13 | 河北工业大学 | A kind of doped nano manganese dioxide composite material, preparation method and applications |
| CN110639542A (en) * | 2019-09-06 | 2020-01-03 | 华南理工大学 | In-situ hybridization room-temperature formaldehyde removal catalyst, composite gel, and preparation method and application thereof |
| CN110639542B (en) * | 2019-09-06 | 2021-04-09 | 华南理工大学 | In-situ hybridization room-temperature formaldehyde removal catalyst, composite gel, and preparation method and application thereof |
| CN110680170A (en) * | 2019-09-24 | 2020-01-14 | 华南理工大学 | Screen window or curtain capable of removing formaldehyde and VOCs and preparation method thereof |
| CN110665539A (en) * | 2019-09-25 | 2020-01-10 | 西南石油大学 | Formula and process of manganese silicate-based ozone removal material |
| CN110560144A (en) * | 2019-09-25 | 2019-12-13 | 西南石油大学 | Preparation method and application of moisture-proof ozone removal catalyst |
| CN110652996B (en) * | 2019-10-22 | 2022-07-22 | 天津大学 | Preparation and application of manganese-containing oxide supported molecular sieve catalyst |
| CN110652996A (en) * | 2019-10-22 | 2020-01-07 | 天津大学 | Preparation and application of manganese-containing oxide supported molecular sieve catalyst |
| CN114618589A (en) * | 2020-12-14 | 2022-06-14 | 大连海事大学 | Preparation method and application of ozone degradation catalyst based on iron-based organic framework |
| CN114618589B (en) * | 2020-12-14 | 2024-04-02 | 大连海事大学 | Preparation method and application of ozone degradation catalyst based on iron-based organic framework |
| CN112604693B (en) * | 2020-12-15 | 2022-03-15 | 南京工业大学 | Mesoporous manganese-based composite oxide and preparation method and application thereof |
| CN112604693A (en) * | 2020-12-15 | 2021-04-06 | 南京工业大学 | Mesoporous manganese-based composite oxide and preparation method and application thereof |
| CN112569928A (en) * | 2020-12-17 | 2021-03-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone-formaldehyde-benzene co-catalytic degradation catalyst and preparation method and application thereof |
| CN112808278A (en) * | 2021-01-07 | 2021-05-18 | 浙江工业大学 | Mixed metal nano-magnetic ozone catalyst for degrading antibiotic wastewater and application |
| CN113413896A (en) * | 2021-07-13 | 2021-09-21 | 西南石油大学 | Ozone decomposition catalyst with natural pyrolusite as carrier and preparation method thereof |
| CN113546641A (en) * | 2021-07-26 | 2021-10-26 | 安徽科浦环保科技有限公司 | Preparation method of composite catalytic material for eliminating ozone |
| CN113877602A (en) * | 2021-11-15 | 2022-01-04 | 青岛华世洁环保科技有限公司 | Household deodorizing material for old people and preparation method thereof |
| CN113877602B (en) * | 2021-11-15 | 2024-02-13 | 青岛华世洁环保科技有限公司 | Household deodorizing material for old people and preparation method thereof |
| CN114618475B (en) * | 2022-04-06 | 2024-04-12 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN114618475A (en) * | 2022-04-06 | 2022-06-14 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN114700082A (en) * | 2022-04-28 | 2022-07-05 | 江苏蓝溪环境科技有限公司 | Preparation method of catalyst for ozone tail gas destruction |
| CN114832810A (en) * | 2022-05-13 | 2022-08-02 | 福州大学 | Amorphous Zr MnO x Preparation method and advanced oxidation application thereof |
| CN115121258A (en) * | 2022-07-28 | 2022-09-30 | 无锡威孚环保催化剂有限公司 | Ozone eliminating catalyst and preparation method thereof |
| CN115487823A (en) * | 2022-10-19 | 2022-12-20 | 西南石油大学 | Preparation method and application of high-humidity-resistance ozonolysis catalyst |
| CN116273027B (en) * | 2023-05-19 | 2023-08-18 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Sulfur-resistant flue gas ozone decomposition catalyst and preparation method and application thereof |
| CN116273027A (en) * | 2023-05-19 | 2023-06-23 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Sulfur-resistant flue gas ozone decomposition catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102600861B (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102600861B (en) | For the manganese base composite oxidate Catalysts and its preparation method of catalytic decomposition ozone | |
| US11684908B2 (en) | Cerium manganese catalyst, preparation method therefor and use thereof | |
| CN108114711B (en) | Transition metal oxide catalyst for catalytic removal of ozone and preparation method thereof | |
| CN102451711B (en) | Industrial wastewater treatment catalyst and preparation method thereof | |
| CN104001502B (en) | Cerium Mn catalyst, the preparation method and its usage of ozone decomposition under a kind of room temperature high humility | |
| CN102600850B (en) | A kind of preparation method of the catalyst of elimination cos and Carbon bisulfide simultaneously | |
| CN101733105B (en) | Carbonyl sulfur hydrolyst prepared by using binary type hydrotalcite as precursor and method for preparing same | |
| CN101690893A (en) | Carbonyl sulfide hydrolysis and preparation method thereof | |
| CN106732509A (en) | The preparation method of modified aluminium oxide supports, catalytic ozone oxidation catalyst and its application | |
| CN107469834A (en) | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method | |
| CN105753907B (en) | A kind of synthetic method of the metal organic framework containing unsaturated coordination mixed valence iron center | |
| CN109574333A (en) | A kind of copper modification nitrogen-doped titanium dioxide material and its preparation method and application | |
| CN106187737A (en) | A kind of method of carbon-supported polynary noble metal catalyst catalytic oxidation of glucose preparation of gluconic acid sodium | |
| CN105709743A (en) | Catalytic wet oxidation catalyst and preparation method thereof. | |
| CN109261164A (en) | A kind of copper, the preparation of cobalt codope manganese-based catalyst and its application in low concentration ozone decomposition | |
| CN105709737B (en) | Catalytic wet oxidation catalyst and its preparation method | |
| CN109225218A (en) | A kind of silver Mn oxide composite catalyst, preparation method and the usage | |
| CN104667936B (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN109126771B (en) | Non-noble metal VOCs catalyst and preparation method thereof | |
| CN112246268A (en) | Novel efficient ozone catalytic material and preparation method thereof | |
| CN104707562A (en) | Method for preparing magnesium-aluminum ion doped mesoporous TiO2 fluorine removal agent | |
| CN105709732A (en) | Noble metal catalyst for catalytic wet oxidation and preparation method thereof | |
| CN106178924B (en) | A kind of preparation method of catalytic cracking fuel gas sulfur transfer additive | |
| CN109174199A (en) | A kind of microwave prepares the method and application of class fenton catalyst and synchronizing regeneration active carbon | |
| JPS6029288B2 (en) | Catalyst manufacturing method and denitrification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211111 Address after: 200333 3rd floor, No. 16, Lane 727, Fuping Road, Putuo District, Shanghai Patentee after: Shanghai Zongsheng enterprise management partnership (limited partnership) Address before: 100085 atmospheric room, No. 18, Shuangqing Road, Haidian District, Beijing Patentee before: Ecological environment research center of Chinese Academy of Sciences |