CN106824218B - A kind of efficient moisture-proof ozone decomposition catalyst and preparation method thereof - Google Patents
A kind of efficient moisture-proof ozone decomposition catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of efficient moisture-proof ozone decomposition catalysts and preparation method thereof, belong to ozone purification catalyst technical field.Efficient moisture-proof ozone decomposition catalyst of the invention is using the oxide of manganese, copper, nickel and cobalt as active component, preparation method is sol-gal process, preparation process is to be dissolved in deionized water and obtain nitrate solution four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate, nitrate solution is slowly added in the mixed solution of citric acid and cationic surfactant, constant temperature stirs to get gel after adjusting the pH value of mixed solution by ammonium hydroxide, and gel is calcined after drying to obtain ozone decomposition catalyst.Preparation method of the invention is simple, at low cost, solves the problems, such as that ozone decomposition catalyst moisture-proof is poor, while improving the efficiency of ozone decomposition, ozone decomposition catalyst long service life, and one month ozone decomposition efficiency of continuous use has no reduction.
Description
Technical field
The invention belongs to ozone purification catalyst technical fields, more specifically, being related to a kind of efficient moisture-proof ozone decomposition
Catalyst and preparation method thereof.
Background technique
Ozone in Air Close To The Earth Surface environment is mainly generated under light illumination by volatile organic matter and nitrogen oxides
Secondary pollution.With reference to " 2015 China Environmental State Bulletin " that Chinese Ministry of Environmental Protection, the People's Republic of China (PRC) issues, Beijing in 2015, on
The industry prosperities area ozone pollution degree such as sea, Jiangsu, Zhejiang, Hebei, Liaoning rose obviously compared to 2014, and multiple areas are smelly
Oxygen evaluate per year regulation calculate, concentration significantly more than defined in " ambient air quality " 160 micrograms/cube limit
Value.In addition, in daily life, printer, duplicator, ultraviolet lamp and all kinds of household electrical appliance that people touch are equal at work
Ozone may be discharged into ambient enviroment, can constitute larger prestige to the health of people after being superimposed with the ozone in atmosphere
The side of body.
Low concentration ozone can be sterilized, be sterilized, but high-concentrated ozone then has high risks to human body, and " Chinese residential area is big
Ozone sanitary standard in gas " GB18066-2000 and " ozone sanitary standard in room air " GB/T18202-2000 provide it is smelly
Oxygen concentration must not be higher than 100 micrograms/cube.According to the correlative study of American National Environmental Protection Agency and the World Health Organization, ozone is dirty
Dye can respiratory system, cardiovascular system, central nervous system etc. to human body cause damages, 24 hour average concentration of ozone often mentions
40 micrograms of liter/cube, it will lead to unusual death rate and promote 0.6%.
In recent years, harm caused by ozone also gradually attracted people's attention, and carried out ozone in the exceeded place of ozone
Purification, which is decomposed, has very significant meaning, at present to the administering method of ozone in air mainly active carbon adsorption, medical fluid
Absorption process, thermal decomposition method, dilution method and catalytic decomposition etc..There are energy consumption height, generation secondary pollution and places for preceding several method
The limitations such as reason amount is small, and ozone, which is catalytically decomposed, can preferably make up the deficiency of above method, can satisfy high de-agglomeration rate, length
The requirement such as phase stabilization, safety, economy, is a kind of side of more satisfactory ozone treatment method and existing most feasibility
Method.
The catalyst decomposed currently used for ozone is mostly to contain transition-metal catalyst and precious metal catalyst containing Mn catalyst
Agent, but often there is preparation process complexity in existing common ozone decomposition catalyst, and at high cost, moisture resistance is poor, and ozone decomposes effect
The problems such as rate is not high, to limit the extensive use of ozone decomposition catalyst.Therefore, it is simple to develop a kind of preparation process,
It is low in cost, and can have with the catalyst of ozone in efficient process environment for the harm for mitigating ozone under different humidity
Great meaning, has a good application prospect simultaneously.
It is existing related public to the patent report of anti humility performance about the decomposition efficiency for improving smelly decomposition catalyst through retrieving
It opens.
Such as, Chinese patent CN1259398A discloses a kind of ozone decomposition catalyst and preparation method thereof, this application
Ozone decomposition catalyst is using active carbon as carrier, with 3~8% (weight) MnO2With the oxidation of 3~8% (weight) nickel or copper or cobalt
Object is active component, is prepared, i.e., the nitrate of manganese nitrate and nickel or copper or cobalt is dissolved in distilled water using dipping-sedimentation,
It immerses dry at 100-120 DEG C after active carbon；It is immersed in the sodium carbonate liquor of 30-40% (weight) again, at 100-120 DEG C
It is dry, through distillation water washing, the dry obtained catalyst at 100-120 DEG C.Chinese Patent Application No. is
201210082986.2, the applying date discloses a kind of for the manganese base of ozone to be catalytically decomposed for the application case on March 26th, 2012
Composite oxide catalysts and preparation method thereof, the catalyst of this application include Mn oxide and at least one oxo transition metal
Compound, preparation method use sluggish precipitation or hydrothermal synthesis method.Using the preparation method of above-mentioned two application case certain
It can be improved the catalytic activity and anti humility performance of catalyst in degree, but application case 1 catalyst for preparing is little in air speed
In the case of (be no more than 20,000), the service life, service life was shorter only by 2000 hours, can not promote.The preparation section of application case 2
For sluggish precipitation or hydrothermal synthesis method, wherein precipitation method process is relative complex, and yield is small, while water-washing process can generate largely
Alkaline waste liquor is not suitable for mass production, and hydro-thermal method needs to use reaction kettle, and heating time is very long, by the limit value of reaction kettle,
Yield is very low, to limit its popularization and application to a certain extent.
For another example, the application case that Chinese Patent Application No. is 201510658187.9 discloses a kind of lanthanum based perovskite type oxidation
Emerging pollutant method in object catalysis ozone degradation water, the preparation of the novel lanthanum based perovskite type oxide catalyst of this application
Steps are as follows: (1) weighing 0~2g cetyl trimethylammonium bromide (CTAB), be dissolved in 10~50ml deionized water at room temperature
In；(2) 2~8mmol lanthanum nitrate and 2~8mmol cobalt nitrate are added in the above solution and stirs, solution is warming up to 60~80
DEG C, and futher stir 30~60 minutes；(3) after solution temperature is reduced to room temperature, 4.0mol/L NaOH to pH, which is added dropwise, is
12~13, solution gradually becomes suspension；(4) suspension is stirred 6~8 hours at 60~80 DEG C, is then stirred at room temperature
It mixes 10~14 hours；(5) dry, the amorphous precursor of step (4) sample obtained is put into baking oven, at 90~110 DEG C
Under crystallization is dried.(6) it calcines, the dried powder obtained through step (5) is calcined 3.8~4.2 hours at 700~800 DEG C；
(7) cooling, it is naturally cooling to room temperature.But the preparation process of this application needs to be added a large amount of NaOH, and the nothing then obtained is fixed
Shape precursor needs are filtered for multiple times, wash, and preparation section is complex, and can generate many alkaline waste liquors and be handled, ring
Border is seriously polluted, is not suitable for batch production.
Summary of the invention
1. technical problems to be solved by the inivention
An object of the present invention be in order to overcome the ozone decomposition efficiency of existing common ozone decomposition catalyst not high, by
The deficiency that ambient humidity is affected provides a kind of efficient moisture-proof ozone decomposition catalyst.Ozone of the invention decomposes catalysis
The decomposition efficiency of agent is higher, and can effectively avoid influence of the ambient humidity to decomposition efficiency, and moisture resistance is preferable.
A second object of the present invention is to provide a kind of preparation method of efficient moisture-proof ozone decomposition catalyst, this method
Simple and easy, at low cost, the decomposition efficiency of the efficient moisture-proof ozone decomposition catalyst of gained is influenced smaller by ambient humidity, uses the longevity
It orders longer.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of efficient moisture-proof ozone decomposition catalyst of the invention, the catalyst are the oxide by manganese, copper, nickel and cobalt
The full active constituent catalyst of composition.
A kind of preparation method of efficient moisture-proof ozone decomposition catalyst of the invention, comprising the following steps:
(1) nitrate of manganese, copper, nickel and cobalt is dissolved in deionized water, is uniformly mixing to obtain nitrate solution；
(2) citric acid and cationic surfactant are successively dissolved in deionized water, it is molten obtains microscopic appearance adjusting
Liquid；
(3) obtained nitrate solution is slowly added to microscopic appearance to adjust in solution, and constant temperature stirs, and passes through ammonium hydroxide tune
The pH value for saving mixed solution forms colloidal sol, continues stirring until forming viscous thick shape gelinite；
(4) the thick shape gelinite of formation is calcined into the efficient moisture-proof ozone decomposition catalyst described in obtaining after dry.
Further, four nitric hydrate manganese, three water are respectively adopted in the nitrate of manganese in the step (1), copper, nickel and cobalt
Close copper nitrate, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate, and four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate
Molar ratio with cabaltous nitrate hexahydrate is (30~80): (10~50): (5~20): (5~20).
Further, the four nitric hydrates manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate
Molar ratio is 50:25:15:10.
Further, in the step (2) substance of citric acid amount be nitrate solution in cationic substance amount
1~4 times；The cationic surfactant is cetyltrimethylammonium hydroxide, tetradecyl trimethyl ammonium chloride
With in Dodecydimethylammonium bronides any one or at least two mixture, the amount of substance is nitrate solution
The 0.01~0.1 of the amount of middle cationic substance.
Further, the amount of the substance of the citric acid is 2 times of the amount of cationic substance in nitrate solution, described
The amount of cationic surfactant substance is 0.05 of the amount of cationic substance in nitrate solution.
Further, the whipping temp in the step (3) is 40~70 DEG C, is by the pH value that ammonium hydroxide adjusts colloidal sol
2~5.
Further, the drying temperature of thick shape gelinite is 110~140 DEG C in the step (4), drying time 1
~2 hours, calcination temperature was 400~600 DEG C, and calcination time is 2~4 hours.
Further, preparation method of the invention further include by fibre active carbon, granular activated carbon, cellular activated carbon,
Ceramic honey comb, honeycomb aluminum plate, molecular sieve, foam nickel screen or ceramic microsphere are dipped in the step of thick shape gelinite that step (3) obtains,
Then it further takes out drying and calcines the ozone decomposition catalyst for obtaining being carried on carrier.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) a kind of efficient moisture-proof ozone decomposition catalyst of the invention, for what is be made of the oxide of manganese, copper, nickel and cobalt
Full active constituent catalyst, ozone decomposition efficiency with higher, and its decomposition efficiency is not influenced by ambient humidity, moisture resistance
Preferably, can be used in decomposing the ozone under different humidity environment.
(2) preparation method of a kind of efficient moisture-proof ozone decomposition catalyst of the invention, is prepared using sol-gal process
Manganese, copper, nickel and cobalt the full active constituent catalyst of oxide, can be improved the activity of active component by adding citric acid, have
There is the catalyst of high-activity component conducive to formation；And by the addition of cationic surfactant, and control suitable soda acid
Degree guarantees the efficiency of catalyst ozone decomposition and its using not by surrounding so as to significantly improve the moisture resistance of catalyst
The influence of ambient humidity.
(3) preparation method of a kind of efficient moisture-proof ozone decomposition catalyst of the invention, by selecting manganese, copper, nickel and cobalt
Oxide optimized as active component, and to the adding proportion of each active component, urged so as to effectively improve
The catalytic activity of agent guarantees its using effect.
(4) preparation method of a kind of efficient moisture-proof ozone decomposition catalyst of the invention, by citric acid, cation form
The technological parameters such as the additive amount of face activating agent and the calcination temperature in preparation process optimize, so as to further
Guarantee the catalytic activity and moisture resistance of gained catalyst.
Specific embodiment
In recent years, as amount of nitrogen oxides and office printing, copier increase, ozone concentration in ambient enviroment
Also it dramatically increases, research shows that the respiratory tract of ozone meeting intense stimulus people causes bronchitis and pulmonary emphysema, also to human skin
In vitamin E play destruction, cause the skin of people to wrinkle, blackspot occur, or even human immunologic function can be destroyed, induce
Lymphocyte chromosome lesion and it is carcinogenic, therefore the improvement of ozone has been to be concerned by more and more people.Catalyst ozone decomposition is made
Exploitation for presently the most effective ozone governing measure, various ozone decomposition catalysts is hot at the research of numerous researchers
Point.
But the preparation process of existing ozone decomposition catalyst is complicated, and higher cost, decomposition efficiency is relatively low, especially right
Ambient humidity is more sensitive, and decomposition efficiency is affected by ambient humidity, to limit the extensive of ozone decomposition catalyst
Using this is also that numerous researchers urgently want the technical problem solved in the course of the research.Inventor is for existing ozone point
The above problem existing for catalyst is solved, by long-term a large amount of experimental study, finally obtains technical solution of the present invention.The present invention
A kind of efficient moisture-proof ozone decomposition catalyst preparation method, comprising the following steps:
(1) it is in molar ratio by four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate
(30~80): (10~50): (5~20): (5~20) are dissolved in deionized water, are uniformly mixing to obtain nitrate solution, gained nitre
Four kinds of cationic manganese ions in acid salt solution, copper ion, nickel ion and cobalt ions concentration be respectively 0.3~0.8molL-1、
0.1~0.5molL-1, 0.05~0.2molL-1With 0.05~0.2molL-1。
(2) citric acid and cationic surfactant are successively dissolved in deionized water, it is molten obtains microscopic appearance adjusting
Liquid, wherein the amount of the substance of citric acid is 1~4 times of the amount of cationic substance in nitrate solution, and the cationic surface is living
Property agent be cetyltrimethylammonium hydroxide, tetradecyl trimethyl ammonium chloride and Dodecydimethylammonium bronides in appoint
It anticipates a kind of or at least two mixtures, the amount of substance is 0.01~0.1 of the amount of cationic substance in nitrate solution.
(3) obtained nitrate solution is slowly added to microscopic appearance to adjust in solution, and is stirred under 40~70 DEG C of constant temperature
It mixes, the pH value for adjusting mixed solution by ammonium hydroxide continues stirring until forming viscous thick shape gelinite to 2~5 formation colloidal sols.
(4) it after the thick shape gelinite of formation being placed in 110~140 DEG C of dryings 1~2 hour, is placed at 400~600 DEG C and forges
2~4 hours are burnt up to efficient moisture-proof ozone decomposition catalyst of the invention, which is the oxide by manganese, copper, nickel and cobalt
The full active constituent catalyst of composition, ozone decomposition efficiency with higher, and its decomposition efficiency is not influenced by ambient humidity,
Moisture resistance is preferable, can be used in decomposing the ozone under different humidity environment.
Specifically, the present invention is using the full active component catalysis of oxide that sol-gal process prepares manganese, copper, nickel and cobalt
Agent is chelated to metal cation in nitrate together, so as to improve active group by addition citric acid as chelating agent
The activity divided, advantageously forms the catalyst with high-activity component.And the present invention is by the addition of cationic surfactant,
And control suitable pH value, make cationic surfactant controlled under suitable acidity and alkalinity environment crystal nucleation, growth and
Agglomeration process can effectively inhibit the reunion between particle, adjust the micromorphology of catalyst in nanoscale, make moisture
Son can pass freely through and ozone is then trapped and is broken down into oxygen, real so as to significantly improve the moisture resistance of catalyst
The efficiency of existing catalyst ozone decomposition is not influenced by humidity, while the use of catalyst will not influence the mesh of ambient humidity
Mark.
Inventor had found by lot of experiments, by selecting the oxide of manganese, copper, nickel and cobalt as active component,
And the adding proportion of each active component is optimized, while being aided with the cooperation of proper content citric acid, so as to have
Effect improves the catalytic activity of catalyst, guarantees its using effect.The present invention is also by citric acid, cationic surfactant
The technological parameters such as the calcination temperature in additive amount and preparation process optimize, so as to be further ensured that gained is urged
The catalytic activity and moisture resistance of agent, wherein when four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and six hydration nitre
The molar ratio of sour cobalt is 50:25:15:10, and the amount of the substance of citric acid is 2 times of the amount of cationic substance in nitrate solution,
Cationic surfactant uses cetyltrimethylammonium hydroxide, and the amount of its substance is cationic object in nitrate solution
The amount of matter 0.05 when gained catalyst catalytic activity and anti humility performance reach optimal combination.
Meanwhile the present invention can also be by fibre active carbon, granular activated carbon, cellular activated carbon, ceramic honey comb, honeycomb aluminum
Plate, molecular sieve, foam nickel screen or ceramic microsphere are dipped in the thick shape gelinite that step (3) obtains, and then further take out drying and calcine
Obtain being carried on the ozone decomposition catalyst on carrier.
To further appreciate that the contents of the present invention, now in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts, are made by the steps to obtain:
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate are dissolved in deionized water,
It is uniformly mixing to obtain nitrate solution, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.5molL-1、0.25mol·L-1、0.15mol·L-1And 0.1molL-1.Citric acid and cetyltrimethylammonium hydroxide is successively molten
Solution obtains microscopic appearance and adjusts solution in deionized water, and wherein the concentration of citric acid is 2molL-1, cetyl trimethyl
The concentration of ammonium hydroxide is 0.05molL-1.Above-mentioned nitrate solution and microscopic appearance are adjusted solution to be slowly mixed together in equal volume
It is stirred afterwards in 55 DEG C of constant temperature；It is 3 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；Continue stirring until forming viscous thick shape
Gelinite.Then it by thick shape gelinite after 130 DEG C 1 hour dry, places in Muffle furnace and calcines 3 hours at 500 DEG C to obtain the final product
To the efficient moisture-proof ozone decomposition catalyst of the present embodiment.
Embodiment 2
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts for loading granular activated carbon, as follows
It is prepared:
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate are dissolved in deionized water,
It is uniformly mixing to obtain nitrate solution, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.5molL-1、0.25mol·L-1、0.15mol·L-1And 0.1molL-1.Citric acid and cetyltrimethylammonium hydroxide is successively molten
Solution obtains microscopic appearance and adjusts solution in deionized water, and wherein the concentration of citric acid is 2molL-1, cetyl trimethyl
The concentration of ammonium hydroxide is 0.05molL-1.Above-mentioned nitrate solution and microscopic appearance are adjusted solution to be slowly mixed together in equal volume
It is stirred afterwards in 55 DEG C of constant temperature；It is 3 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；Continue stirring until forming viscous thick shape
Gelinite；It is sufficiently impregnated being placed in thick shape gelinite by dry high-quality coconut husk granular activated carbon, it is small in 110 DEG C of dryings 1
Shi Hou is placed in Muffle furnace under inert gas protection, and 450 DEG C of calcinings obtain the efficient moisture-proof of load granular activated carbon for 3 hours
Ozone decomposition catalyst.
Embodiment 3
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts for loading ceramic honey comb, make as follows
It is standby to obtain:
Nitrate solution is prepared, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.5molL-1、0.25mol·L-1、0.15mol·L-1And 0.1molL-1, prepare microscopic appearance and adjust solution, wherein the concentration of citric acid
For 2molL-1, the concentration of cetyltrimethylammonium hydroxide is 0.05molL-1.By above-mentioned nitrate solution and microcosmic
Pattern is adjusted after solution is slowly mixed together in equal volume and is stirred in 55 DEG C of constant temperature；It is 3 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；
Continue stirring until forming viscous thick shape gelinite；Thick shape will be placed in by 300 dry mesh cordierite ceramic honey comb pieces
It is sufficiently impregnated in gelinite, after 130 DEG C 1 hour dry, calcined at 500 DEG C in placement Muffle furnace and obtain within 3 hours load bee
The efficient moisture-proof ozone decomposition catalyst of nest ceramics.
Comparative example 1
This comparative example provides a kind of MnOxOzone decomposition catalyst is made by the steps to obtain:
Prepare manganese nitrate solution, concentration 1molL-1；It prepares microscopic appearance and adjusts solution, wherein the concentration of citric acid
For 2molL-1, the concentration of cetyltrimethylammonium hydroxide is 0.05molL-1；By above-mentioned manganese nitrate solution with it is microcosmic
Pattern is adjusted after solution is slowly mixed together in equal volume and is stirred in 55 DEG C of constant temperature；It is 3 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；
Continue stirring until forming viscous thick shape gelinite；By thick shape gelinite after 130 DEG C 1 hour dry, place in Muffle furnace
It is calcined 3 hours at 500 DEG C and obtains MnOxOzone decomposition catalyst.
Comparative example 2
This comparative example provides a kind of efficient ozone decomposition catalyst without resistance to wet process, is made by the steps
It arrives:
Nitrate solution is prepared, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.5molL-1、0.25mol·L-1、0.15mol·L-1And 0.1molL-1；Prepare citric acid solution, concentration 2molL-1.It will be upper
It states after nitrate solution is slowly mixed together in equal volume with citric acid solution and is stirred in 55 DEG C of constant temperature；Ammonium hydroxide adjusting solution ph, which is added dropwise, is
3, form colloidal sol；Continue stirring until forming viscous thick shape gelinite；By thick shape gelinite after 130 DEG C 1 hour dry, put
It sets to calcine 3 hours at 500 DEG C in Muffle furnace and obtains the efficient ozone decomposition catalyst without resistance to wet process.
The ozone decomposition catalyst obtained to Examples 1 to 3, comparative example 1 and comparative example 2 is tested for the property, specific to survey
Strip part is as follows: being 24 ± 2 DEG C using airconditioning control environment temperature；Ozone generator generates certain density ozone, after dilution
It is divided into two-way, is passed through the drexel bottle equipped with pure water all the way, diluted ozone gas is bubbled in bottle makes the opposite of ozone gas
Humidity reaches 100%, and the ozone gas after another way dilution makes relative humidity 0 after the drying tower for loading silica gel is dry,
It is respectively arranged with glass rotameter in all pipelines and adjusts flow；The merging of two-way gas is followed by catalytic tower, and control enters anti-
The relative humidity for answering tower is respectively 40%, 70% and 90%, control ozone concentration be 500 micrograms/cube or so, it is daily to simulate
The high-concentrated ozone gas that can be touched in life；Catalyst reaction air speed is 30000h-1.Ozone decomposition catalyst performance is surveyed
Test result is as follows:
1 embodiment 1-3 of table and comparative example 1, the ozone decomposition catalyst the performance test results of comparative example 2
As can be seen from Table 1, the ozone purification resolution ratio for the catalyst that embodiment 1-3 is prepared is higher, up to 90%
More than, and its resolution ratio plan is not influenced by ambient humidity, moisture resistance is preferable；And the MnO that comparative example 1 obtainsxOzone decomposition is urged
The ozone purification resolution ratio of agent is relatively low, and the catalyst that comparative example 2 obtains is with higher smelly when ambient humidity is lower
Oxygen purifies resolution ratio, but it is affected to the resolution ratio of ozone by ambient humidity, and moisture resistance is poor.
Embodiment 4
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts, are made by the steps to obtain:
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate are dissolved in deionized water,
It is uniformly mixing to obtain nitrate solution, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.8molL-1、0.1mol·L-1、0.05mol·L-1And 0.05molL-1.Citric acid and Dodecydimethylammonium bronides are successively dissolved
It in deionized water, obtains microscopic appearance and adjusts solution, wherein the concentration of citric acid is 1molL-1, dodecyl dimethyl bromine
The concentration for changing ammonium is 0.1molL-1.Above-mentioned nitrate solution and microscopic appearance are adjusted after solution is slowly mixed together in equal volume in 40
The stirring of DEG C constant temperature；It is 2 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；Continue stirring until forming viscous thick shape gelinite.
Then it by thick shape gelinite after 140 DEG C 2 hours dry, is calcined at 400 DEG C in placement Muffle furnace 4 hours and obtains this implementation
The efficient moisture-proof ozone decomposition catalyst of example, ozone decomposition catalyst the performance test results are closer to embodiment 2.
Embodiment 5
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts, are made by the steps to obtain:
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate are dissolved in deionized water,
It is uniformly mixing to obtain nitrate solution, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.3molL-1、0.5mol·L-1、0.2mol·L-1And 0.2molL-1.Citric acid and tetradecyl trimethyl ammonium chloride are successively dissolved in
It in deionized water, obtains microscopic appearance and adjusts solution, wherein the concentration of citric acid is 4molL-1, tetradecyltrimethylammonium chlorination
The concentration of ammonium is 0.01molL-1.Above-mentioned nitrate solution and microscopic appearance are adjusted after solution is slowly mixed together in equal volume in 70
The stirring of DEG C constant temperature；It is 5 that ammonium hydroxide, which is added dropwise, and adjusts solution ph, forms colloidal sol；Continue stirring until forming viscous thick shape gelinite.
Then it by thick shape gelinite after 120 DEG C 1 hour dry, is calcined at 600 DEG C in placement Muffle furnace 2 hours and obtains this implementation
The efficient moisture-proof ozone decomposition catalyst of example, ozone decomposition catalyst the performance test results are closer to embodiment 2.
Embodiment 6
The present embodiment provides a kind of efficient moisture-proof ozone decomposition catalysts, are made by the steps to obtain:
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate are dissolved in deionized water,
It is uniformly mixing to obtain nitrate solution, wherein the concentration of manganese nitrate, copper nitrate, nickel nitrate and cobalt nitrate is respectively 0.5molL-1、0.3mol·L-1、0.2mol·L-1And 0.1molL-1.By citric acid and Dodecydimethylammonium bronides, myristyl
Trimethyl ammonium chloride is successively dissolved in deionized water, is obtained microscopic appearance and is adjusted solution, wherein the concentration of citric acid is
3mol·L-1, the sum of Dodecydimethylammonium bronides and the concentration of tetradecyl trimethyl ammonium chloride are 0.5molL-1.It will
Above-mentioned nitrate solution and microscopic appearance are adjusted after solution is slowly mixed together in equal volume and are stirred in 45 DEG C of constant temperature；It is molten that ammonium hydroxide adjusting is added dropwise
Liquid pH value is 3, forms colloidal sol；Continue stirring until forming viscous thick shape gelinite.It will be placed in by dry foam nickel screen
It is sufficiently impregnated in thick shape gelinite, after 130 DEG C 1 hour dry, calcine at 500 DEG C in placement Muffle furnace 2 hours and obtain
The efficient moisture-proof ozone decomposition catalyst of the load nickel screen of the present embodiment, ozone decomposition catalyst the performance test results and implementation
Example 2 is closer to.
Claims (8)
1. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst, which comprises the following steps:
(1) nitrate of manganese, copper, nickel and cobalt is dissolved in deionized water, is uniformly mixing to obtain nitrate solution；
(2) citric acid and cationic surfactant are successively dissolved in deionized water, obtain microscopic appearance and adjusts solution；
(3) obtained nitrate solution is slowly added to microscopic appearance to adjust in solution, and constant temperature stirs, is adjusted by ammonium hydroxide mixed
The pH value for closing solution forms colloidal sol, continues stirring until forming viscous thick shape gelinite；
(4) calcining after the thick shape gelinite drying of formation is obtained into the full active group being made of the oxide of manganese, copper, nickel and cobalt
Divide efficient moisture-proof ozone decomposition catalyst.
2. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to claim 1, it is characterised in that: described
Manganese in step (1), copper, nickel and cobalt nitrate be respectively adopted four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and
Cabaltous nitrate hexahydrate, and four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate molar ratio be
(30~80): (10~50): (5~20): (5~20).
3. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to claim 2, it is characterised in that: described
Four nitric hydrate manganese, Gerhardite, Nickelous nitrate hexahydrate and cabaltous nitrate hexahydrate molar ratio be 50:25:15:10.
4. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to any one of claim 1-3, special
Sign is: the amount of the substance of citric acid is 1~4 times of the amount of cationic substance in nitrate solution in the step (2)；It is described
Cationic surfactant be cetyltrimethylammonium hydroxide, tetradecyl trimethyl ammonium chloride and dimethyl
In base ammonium bromide any one or at least two mixture, the amount of substance is cationic substance in nitrate solution
The 0.01~0.1 of amount.
5. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to claim 4, it is characterised in that: described
The amount of the substance of citric acid is 2 times of the amount of cationic substance in nitrate solution, the cationic surfactant substance
Amount is 0.05 of the amount of cationic substance in nitrate solution.
6. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to claim 4, it is characterised in that: described
Whipping temp in step (3) is 40~70 DEG C, is 2~5 by the pH value that ammonium hydroxide adjusts colloidal sol.
7. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to claim 6, it is characterised in that: described
In step (4) drying temperature of thick shape gelinite be 110~140 DEG C, drying time be 1~2 hour, calcination temperature be 400~
600 DEG C, calcination time is 2~4 hours.
8. a kind of preparation method of efficient moisture-proof ozone decomposition catalyst according to any one of claim 1-3, special
Sign is: further including by fibre active carbon, granular activated carbon, cellular activated carbon, ceramic honey comb, honeycomb aluminum plate, molecular sieve, foam
Nickel screen or ceramic microsphere are dipped in the step of thick shape gelinite that step (3) obtains, and then further take out drying and calcining is loaded
In the ozone decomposition catalyst on carrier.
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| CN107376926B (en) * | 2017-08-18 | 2020-02-11 | 中国科学院过程工程研究所 | Perovskite type ozonolysis catalyst and preparation method and application thereof |
| CN109012690B (en) * | 2018-09-04 | 2021-10-29 | 建投邢台热电有限责任公司 | Medium-temperature hydrophobic ozonolysis catalyst, application and preparation method of application |
| 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 |
| CN111097420B (en) * | 2018-10-26 | 2021-04-27 | 中国科学院过程工程研究所 | Nickel-based ozonolysis catalyst and preparation method and application thereof |
| CN110813368B (en) * | 2019-11-28 | 2022-08-09 | 上海绿强新材料有限公司 | Preparation method of ozonolysis catalyst in high-humidity tail gas |
| CN111186901B (en) * | 2020-01-24 | 2022-06-03 | 辽宁中舟得水环保科技有限公司 | Technology for feeding ozone into multistage ozone reaction tower by ejector |
| CN111939896B (en) * | 2020-07-30 | 2023-02-03 | 浙江工业大学 | Liquid catalyst for catalyzing ozonolysis at normal temperature and preparation method and application thereof |
| CN113663729B (en) * | 2021-09-01 | 2023-03-31 | 南大恩洁优环境技术(江苏)股份公司 | High-efficiency carbon fiber supported catalyst and preparation method thereof |
| CN116808839B (en) * | 2023-07-03 | 2024-03-19 | 威海智洁环保技术有限公司 | Preparation method and application of ozone catalyst modified ceramic membrane |
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