CN105478106A - Novel manganese dioxide-loaded ceramic-based catalyst and its preparation method and use - Google Patents
Novel manganese dioxide-loaded ceramic-based catalyst and its preparation method and use Download PDFInfo
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- CN105478106A CN105478106A CN201510840270.8A CN201510840270A CN105478106A CN 105478106 A CN105478106 A CN 105478106A CN 201510840270 A CN201510840270 A CN 201510840270A CN 105478106 A CN105478106 A CN 105478106A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a novel manganese dioxide-loaded ceramic-based catalyst and its preparation method and use. The preparation method of the novel manganese dioxide-loaded ceramic-based catalyst comprises mixing a potassium permanganate aqueous solution, a manganese sulfate aqueous solution and a ceramic-based carrier and sintering the mixture at a high temperature. Potassium permanganate and manganese sulfate are dissolved in water and the solution and the ceramic-based carrier are mixed. A part of potassium permanganate directly reacts with manganese sulfate to produce manganese dioxide, the residual potassium permanganate slowly reacts to produce manganese dioxide and the manganese dioxide is uniformly distributed in the carrier. Through use of a swelling agent comprising sodium bicarbonate, ammonium bicarbonate and calcium carbonate, a utilization ratio of a MnO2 active component is improved, a production cost is reduced and large-scale industrial production is easy. Through catalyst catalysis, ozone can effectively remove organic pollutants in water and has a high oxidation capability.
Description
Technical field
The invention belongs to ozone catalyst preparing technical field, particularly a kind of novel load manganese dioxide pottery substrate catalyst and preparation method thereof and application.
Background technology
As far back as 19th century, people have just recognized the strong oxidation of ozone, find that ozone has oxidation to materials such as timber, straw, starch, phytochrome, natural rubber, fat, vegetable and animals oils and alcohol.1868, Dege bass (deGebeth) obtained the Section 1 patent of ozone application technology, with ozone, coal oil mixture was oxidized to the product being suitable for coating, paint use.1873, ozone was refined at sugar and is come into operation in crofting by Europe.Over more than 100 year, ozone application has been deep into multiple field, has made major contribution to the production technology development of the mankind.Ozone application is divided into fresh-keeping and medical four fields of water treatment, chemical oxidation, food processing by purposes, and the application study of every field and equipment development have reached quite high level all.The world has defined independently ozone technology industry and department, and the international ozone association (IOA) of setting up for 1973 is located at Canada.This association every two years once holds international conference and exchanges various countries' development ozone technology
After World War II, ozone application technology has received tremendous development in the world.First, 1902, Paderborn, Germany establishes the extensive water factory of First ozone treatment water quality, has started the beginning of Ozone Water process, and the national waterworks using ozones such as existing thousands of ozone water factories are American-European, Japanese, Canadian in the world reach popularity now.Mineral water, pure water producer are nearly all equipped with ozone devices.U.S.'s early seventies starts to utilize Wastewater Treatment by Ozone, mainly in order to sterilization, removal pollutant, decolouring etc. reach discharge standard.Japan then after water-deficient area is using sewage ozone treatment as in water use.The countries such as U.S., day, moral, method all establish large-scale ozone sewage treatment plant in recent years.
Water treatment ozone generation application technology mainly divides generation, cooling, drying, the large foundation of mixing wastewater with air four and electric-control system, structural system six broad aspect technology.The concentration unit that ozone is used for water treatment is generally calculate by mg/L, and this and air type commonly use mg/m
3differ from 1,000 times, it can thus be appreciated that water treatment needs high concentration, the ozone of large generating capacity could be applied, ozone generating capacity/hour, bearing power power consumption, source of the gas aridity, life of product etc. are its leading indicators.There is many employing bubble-discharge methods in water treatment ozone, because of concentration necessary, its power consumption increases, and the temperature rise of device is also inevitable, and temperature rise affects ozone generation and the principal element of equipment life, so generally need cooling, mainly contain air-cooled, water-cooled two kinds, what have is then solved by cold air source, adopt which kind of mode, determined by equipment de-sign.
At present, be used alone ozonation technology process waste water and still there are some problems.On the one hand, ozone and organic reaction selectivity are comparatively strong, at low dosage with in the short time, and the impossible permineralization pollutant of ozone, and the intermediate product decomposing generation can stop the further oxidation of ozone.The incurred cost of ozone is high in addition, and utilization rate is on the low side, causes disposal cost high.Therefore to the raising utilization rate of ozone and the research of oxidability this respect, be current focus both domestic and external.
In the oxidation efficiency improving ozone, the development of ozone technology is broadly divided into two classes: a kind of be by ozone with as ultrasonic, ultraviolet, be hydrogen peroxide catalyzedly converted into the stronger and hydroxyl radical free radical that reaction selectivity is lower of oxidisability.Another kind of is be that ozone oxidation strengthened by catalyst with solid particle, as active carbon, metal oxide, titanium dioxide, solid particle is catalyst, good catalytic action is had to the oxidation of the ozone in waste water, in the process of water treatment, these solid catalysts are retained in ozone catalytic reactor always and play catalysed oxidn, do not need follow-up separating measure, will have its actual application value.
Burning method is with the metal of solid fraction (slaine and oxide thereof) for catalyst, strengthens ozone oxidation reaction, is the technology of new in recent years.The object of this technology promotes O exactly
3decomposition, to produce free radical isoreactivity intermediate to strengthen ozonisation.The catalyst having copper MnZn calcium class that its key is the making of efficient metallic catalyst and screening, studied and filtered out at present.
The preparation of ozone catalyst heterogeneous at present, the method adopted is: by have the metal nitrate of catalytic activity or sulfate one or more compound is soluble in water by a certain percentage, then add carrier, add alkaline matter, make these metallic salts form precipitation of hydroxide.Then be uniformly mixed, washing and filtering carrier, finally baking is fired standby, because catalyst is attached to carrier surface by such preparation method, there is a large amount of byproducts of reaction in preparation process, the catalyst that simultaneously cannot be attached to carrier surface in a large number needs to be removed by washing, causes larger waste.In addition, because catalyst is attached to carrier surface by baking, therefore its adhesive strength is poor, and the turnover rate repeatedly using rear catalyst is comparatively large, and due to such production method complex steps, more difficultly realizes large-scale industrial production.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, one of the problem to be solved in the present invention is to provide the preparation method of a kind of novel load manganese dioxide pottery substrate catalyst.This preparation method by add in pottery medium carrier production process there is catalytic activity component as its raw materials for production, and utilize the chemical reaction characteristic of two kinds of active components, obtain the manganese dioxide catalytic activity component with catalytic activity, prepare the pottery substrate catalyst of catalytic ozonation, improve ozone oxidation ability, remove hardly degraded organic substance ability in water to improve, thus reduce the operating cost of ozone oxidation water treatment.
Two of the problem to be solved in the present invention is to provide novel load manganese dioxide pottery substrate catalyst prepared by said method.
Three of the problem to be solved in the present invention is to provide the application of above-mentioned novel load manganese dioxide pottery substrate catalyst in water treatment.
The present invention seeks to be achieved through the following technical solutions:
A kind of preparation method of novel load manganese dioxide pottery substrate catalyst: potassium permanganate solution, manganese sulfate solution are mixed with pottery medium carrier, high temperature sintering.
Preferably, described pottery medium carrier is at least one in flyash, kaolin and swelling agent.
More preferably, described pottery medium carrier is mixed by following weight parts raw material: flyash 40-60 part, kaolin 30-40 part, swelling agent 10-20 part.
Preferably, described swelling agent is at least one in sodium acid carbonate, carbonic hydroammonium and calcium carbonate.
More preferably, described swelling agent is the mixture of sodium acid carbonate, carbonic hydroammonium and calcium carbonate, and the mass ratio of described sodium acid carbonate, carbonic hydroammonium, calcium carbonate is (1-3): (1-3): (1-3).
Preferably, the mass ratio of described pottery medium carrier, potassium permanganate and manganese sulfate is 1:(0.002-0.005): (0.004-0.02).
Preferably, in described potassium permanganate solution, the concentration of potassium permanganate is 0.5-5wt%, and in manganese sulfate solution, the concentration of manganese sulfate is 2-12wt%.
Preferably, during described high temperature sintering, sintering temperature is 1100-1250 DEG C, and sintering time is 1-12 hour.
Present invention also offers a kind of novel load manganese dioxide pottery substrate catalyst, adopt said method to be prepared from.
The active component of described catalyst is MnO
2, carrier is Tao Jizhi.This catalyst, when carrying out catalytic reaction, had both played the effect improving ozone oxidation ability, again because be solid particle, formed the oxidation reaction of heterocatalysis ozone, thus can reuse, and reduced secondary pollution and not easily ran off again cause secondary pollution to waste water.
Present invention also offers the application of above-mentioned novel load manganese dioxide pottery substrate catalyst in water treatment.
This novel load manganese dioxide pottery substrate catalyst both can process water separately, also can with additive method coupling.Ozone is after the catalysis of this novel load manganese dioxide pottery substrate catalyst, and more effectively can remove organic pollutants, its oxidability is significantly improved, thus reduces the dosage of ozone, saves operating cost; Be there is by preparation top layer the pottery substrate catalyst of the load manganese dioxide enriching micropore, greatly can improve catalyst utilization, reduce the production cost of catalyst, reduce catalyst loss rate, prevent secondary pollution.
Mechanism of the present invention is:
The raw material that pottery medium carrier is produced is all dusty raw materials, by mixing with water, must form carrier blank, forming pottery medium carrier through sintering in production process.The present invention is by soluble in water for the potassium permanganate and manganese sulfate with ozone catalytic activity, obtain the aqueous solution of potassium permanganate and manganese sulfate, be used for replacing manufacturing the water of pottery medium carrier blank, and obtained carrier blank, through high temperature sintering, obtain load manganese dioxide pottery substrate catalyst.
Use potassium permanganate and manganese sulfate solution as binding agent, because its material is close, therefore its adhesive strength is high, makes remaining support material be attached to support material core surface, obtains the pottery medium carrier that particle diameter increases.
Potassium permanganate and manganese sulfate add simultaneously, a part directly carries out chemical reaction, form small manganese dioxide, be attached on carrier, the potassium permanganate that a part is residual and manganese sulfate are present in carrier, and potassium permanganate oneself is comparatively unstable, slowly redox generates manganese dioxide, and the manganese sulfate in manganese sulfate solution is when temperature is higher than 800 DEG C, be decomposed into the gas such as MnO2 and sulfur dioxide, gas discharges after treatment with the tail gas of heating furnace.And the MnO2 particle be decomposed to form is tiny, be uniformly distributed in haydite, improve the utilization rate of MnO2 active component.
The present invention by potassium permanganate and manganese sulfate soluble in water, as binding agent, with make pottery medium carrier be mixed to form carrier stock; Potassium permanganate is through reacting with manganese sulfate, and self-redox, generate manganese dioxide, manganese sulfate is at high temperature decomposed into the gas such as MnO2, sulfur dioxide, gas discharges after treatment with the tail gas of heating furnace, and the MnO2 particle be decomposed to form is tiny, is uniformly distributed in pottery medium carrier, improves the utilization rate of MnO2 active component.Active component due to catalyst is with the aqueous solution and makes pottery medium carrier mixing back loading on support material core, and because its material is close, therefore its adhesive strength is high, simultaneously by once sintered shaping.
The present invention by by potassium permanganate and manganese sulfate water-soluble, then with pottery medium carrier mix, the potassium permanganate of a part directly and manganese sulfate react and generate manganese dioxide, residual potassium permanganate slowly reacts generation manganese dioxide, residual manganese sulfate is through high-temperature sintering process, decompose the MnO2 particle obtained tiny, be uniformly distributed in carrier, and by adopting sodium acid carbonate, carbonic hydroammonium, the swelling agent that calcium carbonate three is composite, improve the utilization rate of MnO2 active component, reduce production cost, be easy to realize large-scale industrial production, ozone is after catalyst, more effectively can remove organic pollutants, its oxidability significantly improves.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, the following stated, only to preferred embodiment of the present invention, not do other forms of restriction to the present invention, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed to the Equivalent embodiments of equal change.Everyly do not depart from the present invention program's content, any simple modification done following examples according to technical spirit of the present invention or equivalent variations, all drop in protection scope of the present invention.
The each raw material introduction of embodiment:
Potassium permanganate, No. CAS: 7722-64-7.
Manganese sulfate, No. CAS: 7785-87-7.
Kaolin, No. CAS: 1332-58-7.
Sodium acid carbonate, No. CAS: 144-55-8.
Carbonic hydroammonium, No. CAS: 1066-33-7.
Calcium carbonate, No. CAS: 471-34-1.
Flyash, the model adopting Hebei Bo Tai building materials Science and Technology Ltd. to produce is the flyash of 100.
embodiment 1
Pottery medium carrier: get flyash 5kg, kaolin 3.5kg, sodium acid carbonate 0.5kg, carbonic hydroammonium 0.5kg, calcium carbonate 0.5kg mix and get final product.
The preparation method of novel load manganese dioxide pottery substrate catalyst, comprises following concrete steps:
(1) distinguish soluble in water by potassium permanganate and manganese sulfate, obtain potassium permanganate solution and manganese sulfate solution respectively, wherein in potassium permanganate solution, the concentration of potassium permanganate is 2.5wt%, and in manganese sulfate solution, the concentration of manganese sulfate is 5.0wt%.
(2) 50wt% getting pottery medium carrier total amount prepares by sugar-coat draft machine the haydite materials core that particle diameter is 2.5mm; Get potassium permanganate solution 0.96kg(and potassium permanganate addition is 0.024kg), manganese sulfate solution 0.96kg(and manganese sulfate addition be 0.048kg) mix with residue 50wt% medium carrier of making pottery, obtain mixture; Then joined by mixture to prepare to have in the sugar-coat draft machine of haydite materials core and mix with haydite materials core, mixture is attached on above-mentioned haydite materials core, and generating particle diameter is the haydite of 5mm; Sinter at 1200 DEG C, sintering time is 3 hours, prepares described novel load manganese dioxide pottery substrate catalyst.
embodiment 2
Pottery medium carrier: get flyash 5kg, kaolin 3.5kg, sodium acid carbonate 0.5kg, carbonic hydroammonium 0.5kg, calcium carbonate 0.5kg mix and get final product.
The preparation method of novel load manganese dioxide pottery substrate catalyst, comprises following concrete steps:
(1) potassium permanganate is soluble in water, obtain potassium permanganate solution wherein in potassium permanganate solution the concentration of potassium permanganate be 2.5wt%.
(2) 50wt% getting pottery medium carrier total amount prepares by sugar-coat draft machine the haydite materials core that particle diameter is 2.5mm; Get potassium permanganate solution 2.88kg(and potassium permanganate addition is 0.072kg) mix with residue 50wt% medium carrier of making pottery, obtain mixture; Then joined by mixture to prepare to have in the sugar-coat draft machine of haydite materials core and mix with haydite materials core, mixture is attached on above-mentioned haydite materials core, and generating particle diameter is the haydite of 5mm; Sinter at 1200 DEG C, sintering time is 3 hours, prepares described novel load manganese dioxide pottery substrate catalyst.
embodiment 3
Pottery medium carrier: get flyash 5kg, kaolin 3.5kg, sodium acid carbonate 0.5kg, carbonic hydroammonium 0.5kg, calcium carbonate 0.5kg mix and get final product.
The preparation method of novel load manganese dioxide pottery substrate catalyst, comprises following concrete steps:
(1) manganese sulfate is soluble in water, obtain manganese sulfate solution, wherein in manganese sulfate solution, the concentration of manganese sulfate is 5.0wt%.
(2) 50wt% getting pottery medium carrier total amount prepares by sugar-coat draft machine the haydite materials core that particle diameter is 2.5mm; Get manganese sulfate solution 1.44kg(and manganese sulfate addition is 0.072kg) mix with residue 50wt% medium carrier of making pottery, obtain mixture; Then joined by mixture to prepare to have in the sugar-coat draft machine of haydite materials core and mix with haydite materials core, mixture is attached on above-mentioned haydite materials core, and generating particle diameter is the haydite of 5mm; Sinter at 1200 DEG C, sintering time is 3 hours, prepares described novel load manganese dioxide pottery substrate catalyst.
embodiment 4
Prepare novel load manganese dioxide pottery substrate catalyst by the method for embodiment 1, difference is only: pottery medium carrier: get flyash 5kg, kaolin 3.5kg, sodium acid carbonate 0.75kg, carbonic hydroammonium 0.75kg mix and get final product.Obtain the novel load manganese dioxide pottery substrate catalyst of embodiment 4.
embodiment 5
Prepare novel load manganese dioxide pottery substrate catalyst by the method for embodiment 1, difference is only: pottery medium carrier: get flyash 5kg, kaolin 3.5kg, sodium acid carbonate 0.75kg, calcium carbonate 0.75kg mix and get final product.Obtain the novel load manganese dioxide pottery substrate catalyst of embodiment 5.
embodiment 6
Prepare novel load manganese dioxide pottery substrate catalyst by the method for embodiment 1, difference is only: pottery medium carrier: get flyash 5kg, kaolin 3.5kg, carbonic hydroammonium 0.75kg, calcium carbonate 0.75kg mix and get final product.Obtain the novel load manganese dioxide pottery substrate catalyst of embodiment 5.
embodiment 7
The application of novel load manganese dioxide pottery substrate catalyst in water treatment:
Utilize the waste water of ozone oxidation advanced treating Coal Chemical Industry after secondary biochemical treatment (COD is 112mg/L), ozone dosage is 56mg/L, wherein 6 groups of novel load manganese dioxide pottery substrate catalyst catalysis adding above-described embodiment 1-6 and prepare, novel load manganese dioxide pottery substrate catalyst dosage is 5mg/L, and comparative example does not add novel load manganese dioxide pottery substrate catalyst.30min post processing effect is in table 1.
Table 1: coal chemical industrial waste water COD treatment effect table
| COD，mg/L | |
| Embodiment 1 | 40 |
| Embodiment 2 | 62 |
| Embodiment 3 | 68 |
| Embodiment 4 | 46 |
| Embodiment 5 | 44 |
| Embodiment 6 | 43 |
| Comparative example | 71 |
Obviously can be found out by table 1, under same ozone dosage, add the obtained novel load manganese dioxide pottery substrate catalyst COD treatment effect of embodiment 1-6 apparently higher than comparative example.Comparing embodiment 1-3, embodiment 1(adopt potassium permanganate and manganese sulfate to mix with pottery medium carrier) COD treatment effect adopts potassium permanganate or manganese sulfate to mix with pottery medium carrier apparently higher than embodiment 2-3(); Comparing embodiment 1 and embodiment 4-6, embodiment 1(swelling agent adopt sodium acid carbonate, carbonic hydroammonium, calcium carbonate composite) COD treatment effect apparently higher than embodiment 4-6(swelling agent adopts any in sodium acid carbonate, carbonic hydroammonium, calcium carbonate both composite).
embodiment 8
The application of novel load manganese dioxide pottery substrate catalyst in water treatment:
Utilize ozone Oxidation Treatment chemical plant phenol wastewater (COD is 331mg/L), ozone dosage is 331mg/L, wherein 6 groups of novel load manganese dioxide pottery substrate catalyst catalysis adding above-described embodiment 1-6 and prepare, novel load manganese dioxide pottery substrate catalyst dosage is 30mg/L, and comparative example does not add novel load manganese dioxide pottery substrate catalyst.30min post processing effect is in table 2.
Table 2: phenol wastewater COD treatment effect table
| COD，mg/L | |
| Embodiment 1 | 78 |
| Embodiment 2 | 114 |
| Embodiment 3 | 141 |
| Embodiment 4 | 96 |
| Embodiment 5 | 90 |
| Embodiment 6 | 87 |
| Comparative example | 219 |
Obviously can be found out by table 2, under same ozone dosage, add the obtained novel load manganese dioxide pottery substrate catalyst COD treatment effect of embodiment 1-6 apparently higher than comparative example.Comparing embodiment 1-3, embodiment 1(adopt potassium permanganate and manganese sulfate to mix with pottery medium carrier) COD treatment effect adopts potassium permanganate or manganese sulfate to mix with pottery medium carrier apparently higher than embodiment 2-3(); Comparing embodiment 1 and embodiment 4-6, embodiment 1(swelling agent adopt sodium acid carbonate, carbonic hydroammonium, calcium carbonate composite) COD treatment effect apparently higher than embodiment 4-6(swelling agent adopts any in sodium acid carbonate, carbonic hydroammonium, calcium carbonate both composite).
Novel load manganese dioxide pottery substrate catalyst in above-described embodiment carries out O3 catalytic oxidation organic pollutants by joining in ozone catalytic reaction unit.Ozone catalytic reaction unit is by water distribution system, catalytic reaction layer, outlet system, tail gas absorber forms, wherein water distribution system realizes by arranging water-locator above filter plate, solid-phase catalyst composition catalytic reaction layer is full of above filter plate, outlet system loads filter screen and makes to be with the carrier of catalyst not taken out of, the ozone that tail gas absorber is residual after collecting reaction.The ozone collected can be applied in other oxidation operation, if ozone is not recycled, is then processed ozone by ozone tail gas destructor, and overflowing to prevent ozone pollutes.Its technological process is that ozone first makes mixing wastewater with air even via gas absorber, then ozone catalytic reaction unit is entered, through water distribution system, water is fully contacted with ozone, catalyst, then catalyst ozone oxidation water pollutant, improve ozone to the removal ability of pollutant, thus save ozone dosage, reduce water treatment operating cost.
Ozone catalytic reactor can be divided into up flow type (water flows from the bottom up) and downflow system (water flows from top to bottom) two kinds according to water (flow) direction, can adjust according to Practical Project.
The technological parameter of this catalytic reactor is as follows: catalyst is full of catalyst reaction device, and the protection height of reserved 0.2-1m, is beneficial to the expansion of up flow type reaction time catalizer layer above; Entering catalytic reactor rapidly after waste water and ozone mixing, is 5-60min with the time of contact of catalyst.
The material of reactor makes with the material of resistance to ozone corrosion, as stainless steel, glass, and polytetrafluoroethylene (PTFE) etc.
Claims (10)
1. a preparation method for novel load manganese dioxide pottery substrate catalyst, is characterized in that, potassium permanganate solution, manganese sulfate solution are mixed with pottery medium carrier, high temperature sintering.
2. the preparation method of novel load manganese dioxide pottery substrate catalyst according to claim 1, it is characterized in that, described pottery medium carrier is at least one in flyash, kaolin and swelling agent.
3. the preparation method of novel load manganese dioxide pottery substrate catalyst according to claim 2, it is characterized in that, described pottery medium carrier is mixed by following weight parts raw material: flyash 40-60 part, kaolin 30-40 part, swelling agent 10-20 part.
4. the preparation method of novel load manganese dioxide pottery substrate catalyst according to claim 3, it is characterized in that, described swelling agent is at least one in sodium acid carbonate, carbonic hydroammonium and calcium carbonate.
5. the preparation method of novel load manganese dioxide pottery substrate catalyst according to claim 4, it is characterized in that, described swelling agent is the mixture of sodium acid carbonate, carbonic hydroammonium and calcium carbonate, and the mass ratio of described sodium acid carbonate, carbonic hydroammonium, calcium carbonate is (1-3): (1-3): (1-3).
6. the preparation method of the novel load manganese dioxide pottery substrate catalyst according to any one of claim 1-5, it is characterized in that, the mass ratio of described pottery medium carrier, potassium permanganate and manganese sulfate is 1:(0.002-0.005): (0.004-0.02).
7. the preparation method of the novel load manganese dioxide pottery substrate catalyst according to any one of claim 1-5, it is characterized in that, in described potassium permanganate solution, the concentration of potassium permanganate is 0.5-5wt%, and in manganese sulfate solution, the concentration of manganese sulfate is 2-12wt%.
8. the preparation method of the novel load manganese dioxide pottery substrate catalyst according to any one of claim 1-5, it is characterized in that, during described high temperature sintering, sintering temperature is 1100-1250 DEG C, and sintering time is 1-12 hour.
9. a novel load manganese dioxide pottery substrate catalyst, it is characterized in that, the method according to any one of claim 1-8 is prepared from.
10. the application in water treatment of novel load manganese dioxide pottery substrate catalyst according to claim 9.
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| CN108579729A (en) * | 2018-03-22 | 2018-09-28 | 清华大学 | The preparation method of catalyst for ozone decomposed |
| WO2019179109A1 (en) * | 2018-03-22 | 2019-09-26 | 清华大学 | Preparation method for catalyst for ozone decomposition |
| US11364483B2 (en) | 2018-03-22 | 2022-06-21 | Tsinghua University | Method for making catalyst for ozone decomposition |
| CN109865536A (en) * | 2018-09-11 | 2019-06-11 | 武汉科技大学 | A kind of method of useless SCR catalyst resource utilization |
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Application publication date: 20160413 |