CN105688912B - A kind of honeycomb fashion preparation method of the ozone oxidation catalyst and its catalyst of preparation - Google Patents
A kind of honeycomb fashion preparation method of the ozone oxidation catalyst and its catalyst of preparation Download PDFInfo
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- CN105688912B CN105688912B CN201610157431.8A CN201610157431A CN105688912B CN 105688912 B CN105688912 B CN 105688912B CN 201610157431 A CN201610157431 A CN 201610157431A CN 105688912 B CN105688912 B CN 105688912B
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- ozone oxidation
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 82
- 230000003647 oxidation Effects 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000000945 filler Substances 0.000 claims abstract description 95
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 93
- 230000001413 cellular effect Effects 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000006210 lotion Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000853 adhesive Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000010802 sludge Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- -1 propylene dimethyl Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003864 humus Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims 1
- 230000037237 body shape Effects 0.000 claims 1
- 229920001249 ethyl cellulose Polymers 0.000 claims 1
- 235000019325 ethyl cellulose Nutrition 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000010865 sewage Substances 0.000 abstract description 40
- 230000000694 effects Effects 0.000 abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- 238000006385 ozonation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 238000005273 aeration Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 239000011295 pitch Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Abstract
The embodiment of the invention discloses a kind of cellular preparation methods of ozone oxidation catalyst and its catalyst of preparation, preparation method to include：Iron carbon filler is crushed, powder shaped iron carbon filler is obtained；According to mass ratio it is (6 16) by the powder shaped iron carbon filler and forming agent, adhesive：(2‑12)：The ratio of (1 4) mixes, and stirring obtains lotion mixture；The lotion mixture is subjected to extrusion forming processing, obtains cellular idiosome；The cellular idiosome is dried, calcination process obtains cellular ozone oxidation catalyst.There is a large amount of pore passage structure in the cellular ozone oxidation catalyst prepared using this programme, large specific surface area, excellent catalytic effect, effect using the honeycomb fashion ozone oxidation catalyst catalysis ozone treated sewage is good, the removal rate of the COD (COD) of sewage is greatly improved, catalyst activity component stripping quantity substantially reduces.
Description
Technical field
The present invention relates to field of catalyst preparation, more particularly to the preparation method of a kind of cellular ozone oxidation catalyst and
Its catalyst prepared.
Background technology
Ozone is a kind of oxidant that oxidability is extremely strong, and the extremely strong antozone of oxidability is generated after decomposing in water
(O) and the oxidation intermediates such as hydroxyl radical free radical (OH) it, is reacted with the organic and inorganic pollution in sewage, reaches deodorization, de-
Color, sterilization and organics removal purpose.But ozone has certain selectivity to the oxidation of pollutant, in particular for those
Chemical constitution is complicated, is difficult to the organic pollution being biodegradable, and cannot carry out effective oxidation processes.In order to make up ozone oxygen
This defect of change technology, catalytic ozonation technology are come into being.
Catalytic ozonation technology is as a kind of efficient, practical, non-secondary pollution high-level oxidation technology, in the difficult drop of processing
The field of sewage of solution is with a wide range of applications, and is the research hotspot of sewage treatment field in recent years.Currently, this technology is
It is extended to O3/H2O2Oxidation, UV/O3Oxidation, UV/H2O2/O3Oxidation, ultrasonically catalyzing ozone oxidation, microwave catalysis ozone oxidation, gold
A variety of high-level oxidation technologies such as category and its oxide catalyst ozone oxidation.
Metal and its oxide catalyst ozonation technology are one kind with solid metal, metal oxide or are supported on carrier
On metal or metal oxide be ozone oxidation catalyst, in low-temp low-pressure even under normal temperature and pressure conditions, you can by those
High-level oxidation technology that is complicated, being difficult to the organic pollution oxygenolysis being biodegradable.But at this stage, using this
Technology is relatively low to the removal rate of the COD (COD) of sewage, is only about 20%-40%, used ozone oxidation catalysis
The catalyst activity component stripping quantity of agent is also higher, be easy to cause secondary pollution.
Invention content
The embodiment of the invention discloses a kind of cellular preparation method of ozone oxidation catalyst and its catalyst of preparation,
To solve the removal rate of existing metal and its oxide catalyst ozonation technology to the COD (COD) of sewage
It is low, the high problem of the active component stripping quantity of ozone oxidation catalyst.Technical solution is as follows：
A kind of preparation method of honeycomb fashion ozone oxidation catalyst, including：
Iron carbon filler is crushed, powder shaped iron carbon filler is obtained；
According to mass ratio it is (6-16) by the powder shaped iron carbon filler and forming agent, adhesive：(2-12)：(1-4's)
Ratio mixes, and stirring obtains lotion mixture；
The lotion mixture is subjected to extrusion forming processing, obtains cellular idiosome；
The cellular idiosome is dried, calcination process obtains cellular ozone oxidation catalyst.
Wherein, the iron carbon filler is discarded iron carbon filler；
It is described by iron carbon filler crush including：It will dry after the discarded iron carbon filler washing, first crushed
It is 3-10 millimeters of iron carbon filler at grain size, then is crushed into powder shaped iron carbon filler.
Wherein, the grain size of the powder shaped iron carbon filler is 0.01-0.50 millimeters.
Wherein, the forming agent is dewatered sludge, and the dewatered sludge includes：Primary deposition by dehydration is dirty
One or more of mud, residual active sludge, humus sludge, digested sludge, chemical sludge, the water content of the dewatered sludge
For the 20%-90% of the dewatered sludge gross mass.
Wherein, the dewatered sludge contains the metal or metal oxide for capableing of O3 catalytic oxidation.
Wherein, described adhesive includes：Sodium metasilicate, epoxy resin, polyvinyl alcohol, lignin, polyacrylamide, poly- dipropyl
It is one or more in alkene dimethyl amine, polydimethyl diallyl ammonium chloride, polyethylene, hydroxyethyl cellulose.
Wherein, the cellular idiosome is porous structure, and pitch of holes is 3-10 millimeters, and hole wall thickness is 1-5 millimeters.
Wherein, the drying is specially：It is 5-24 hours dry under the conditions of temperature is 60-150 DEG C；The calcination process
Specially：Under the conditions of temperature is 300-600 DEG C, roast 2-8 hours.
A kind of cellular ozone oxidation catalyst prepared by above-mentioned preparation method.
Wherein, specific surface area >=150m of the cellular ozone oxidation catalyst2/ g, compression strength ＞ 300N, abrasion
Rate≤0.3%.
As seen from the above technical solution, the preparation side of a kind of cellular ozone oxidation catalyst provided in an embodiment of the present invention
Method and its catalyst of preparation are mixed to get by the powder shaped iron carbon filler obtained after crushing with forming agent, adhesive
It after lotion mixture extrusion forming, is dried, calcination process, obtains cellular ozone oxidation catalyst, due to iron carbon filler
In contain activated carbon, make that there is a large amount of pore passage structure in ozone oxidation catalyst obtained cellular, large specific surface area, catalysis
Effect is good, and the effect using the honeycomb fashion ozone oxidation catalyst catalysis ozone treated sewage is good, to the COD of sewage
(COD) removal rate greatly improves, on the other hand, since there is iron carbon filler iron and metallic catalyst to contain shape together with charcoal
At the iron carbon structure of framework formula, iron, metallic catalyst and charcoal are integrated, are not readily separated, and catalyst activity component stripping quantity is big
It is big to reduce, do not easily cause secondary pollution.
Specific implementation mode
The present invention provides a kind of cellular preparation method of ozone oxidation catalyst and its catalyst of preparation, the preparations
Method can specifically include following steps：
Iron carbon filler is crushed, powder shaped iron carbon filler is obtained；
According to mass ratio it is (6-16) by the powder shaped iron carbon filler and forming agent, adhesive：(2-12)：(1-4's)
Ratio mixes, and stirring obtains lotion mixture；
The lotion mixture is subjected to extrusion forming processing, obtains cellular idiosome；
The cellular idiosome is dried, calcination process obtains cellular ozone oxidation catalyst.
Iron carbon filler is a kind of integrated alloy formed by high melt by multi-element metal fusion multiple catalysts, tool
There is framework to decline pore structure, typically contain iron, carbon and various metals catalyst, for carrying out microelectrolysis processing to sewage, goes
Except the organic pollution in sewage.Iron carbon filler used in the present invention can be the iron carbon filler that arbitrary market is bought, such as can
To be：The specification of the Shandong safe and sound Environmental Protection Technology Co., Ltd of dragon is LAT-TC, and grain size is the iron carbon filler of 1*3cm；Jiangsu Lu Bo
Environment-friendly materials Co., LtdIron carbon filler；The model 8* in Dengfeng City towns Lu Dian Henan and environment-friendly materials factory
The iron carbon filler of 10mm；The iron carbon filler of the model 14-18mm of Pingxiang Tuo Bu Environmental Protection Technology Co., Ltd；The fertile profit of the general mattress in Shandong
The iron carbon filler of the model 1*3cm of Environmental Protection Technology Co., Ltd, is not specifically limited herein.Since iron carbon filler is usually grain
Diameter is the particulate filler of the shapes such as oblateness, spherical shape or porous column shape of Centimeter Level, is unsuitable for directly preparing above-mentioned honeycomb fashion smelly
Oxygen oxidation catalyst first crushes iron carbon filler so generally requiring, and obtains powder shaped iron carbon filler, can specifically pass through
The mode of mechanical crushing, it is 0.01-0.50 that iron carbon filler, which is fully ground into grain size, for example, by using ball-milling method or comminution by gas stream
The powder shaped iron carbon filler of millimeter, in favor of the progress of subsequent preparation process.Above-mentioned grinding mode is to compare in the prior art
More common technology, the present invention is herein without specifically describing.
It should be noted that iron carbon filler used in the present invention can be discarded iron carbon filler, described is discarded
Iron carbon filler is the iron carbon filler for failing discarded in microelectrolysis processing sewage technique.Although discarded iron carbon filler is at light electrolysis
It cannot be used continuously in reason sewage technique, but inventor is found surprisingly that, discarded iron carbon filler can be catalyzed smelly well
Oxygen aoxidizes, and the recycling of resource may be implemented using discarded iron carbon filler, while substantially reducing the honeycomb fashion ozone oxidation
The manufacturing cost of catalyst.Since discarded iron carbon filler surface is generally attached with some pollutants, suspended matter etc., it is possible to
Discarded iron carbon filler is pre-processed, specific pretreated mode can be：It will be dried after discarded iron carbon filler washing,
It is 3-10 millimeters of iron carbon filler to be first ground into grain size, then is crushed into powder shaped iron carbon filler, and washing process can be with
By removals such as discarded pollutant, the suspended matters on iron carbon filler surface, make the original pore passage structure release of discarded iron carbon filler
Out, specific washing times are cleaned up with the iron carbon filler that will be discarded and are advisable, and are not specifically limited herein, such as can will be given up
The iron carbon filler abandoned is washed 2-5 times with clear water.Drying and processing specifically may be used 5-24 hours dry in 50-90 DEG C of baking oven
Mode so that washing after discarded iron carbon filler be completely dried.There may be plates in discarded iron carbon filler after drying
Tie phenomenon, crushing effect may be influenced by directly crushing processing at this time, so as to get powder shaped iron carbon filler grain size it is uneven
Even, to avoid the appearance of this problem, it is 3-10 millimeters that can the discarded iron carbon filler after drying be first ground into grain size
Iron carbon filler keeps hardened iron carbon filler broken, is further ground into the powder shaped iron that grain size is 0.01-0.50 millimeters
Carbon filler.
After obtaining above-mentioned powder shaped iron carbon filler, it is mixed with forming agent, adhesive, stirred, it is mixed that lotion can be obtained
Close object.In practical application, inventor has found that by powder shaped iron carbon filler and forming agent, adhesive be (6-16) according to mass ratio：
(2-12)：Mixed effect is preferable when (1-4) is mixed, and obtained lotion mixture is relatively suitable for the processing of subsequent extrusion forming.On
Adhesion strength between powder shaped iron carbon filler and forming agent can be increased by stating adhesive, keep molding effect more preferable, generally can be with
Select sodium metasilicate, epoxy resin, polyvinyl alcohol, lignin, polyacrylamide, the poly- two propylene dimethyl that can be used for adhesive
It is one or more in amine, polydimethyl diallyl ammonium chloride, polyethylene, hydroxyethyl cellulose, and can be used for adhesive
Above-mentioned substance is the prior art, for the technician, is easy to get, and therefore, the present invention is not herein to above-mentioned object
Matter is defined and illustrates one by one.
In practical application, forming agent may include yellow mud, sesbania powder, diatomite, sludge, aluminium oxide etc., it is preferred to use de-
For sewage sludge as forming agent, described dewatered sludge refers to the sludge isolated in wastewater treatment process；Sludge is returned again
It receives and utilizes, manufacturing cost can be further decreased, solve the handling problems of sludge, in addition, typically containing bacterium, micro- life in sludge
Contain some glycoprotein in object and clay, bacterium and microorganism, adhesive and extrusion aid can be played the role of, conducive to cream is obtained
Body mixture and the processing of subsequent extrusion forming.The dewatered sludge can be the primary deposition sludge by dehydration, residue
One or more of activated sludge, humus sludge, digested sludge, chemical sludge, described primary deposition sludge are：It is first heavy
The sediment retained in the pond of shallow lake, may include physical sedimentation sludge, coagulated sludge and chemically precipitated sludge, in order to not influence
The preparation of cellular ozone oxidation catalyst and catalytic effect, the general primary deposition sludge less using pollutant, without making
With the sludge after multiple precipitation.Described residual active sludge is：In Wastewater Treated by Activated Sludge Process sewage technique, what secondary settling tank generated
Sediment.Described humus sludge is：Using biofilm (such as biofilter, biological rotating disk, part biological contact-oxidation pool
Deng) in sewage treatment, sediment that secondary sedimentation tank generates.Described chemical sludge is：Coagulating kinetics natural water
With the sludge of trade effluent discharge.Since the water content of above-mentioned sludge is generally higher, the mixing of lotion mixture may be influenced
The effect of effect and subsequent extrusion forming processes, it is possible to above-mentioned sludge is carried out dehydrating to obtain dewatered sludge, made
Its water content reaches the 20%-90% of dewatered sludge gross mass.
Further, in preparation method provided by the present invention, it is preferred to use contain the metal for capableing of O3 catalytic oxidation
Or the dewatered sludge of metal oxide is as forming agent.It is using containing metal or metal oxygen with O3 catalytic oxidation effect
During compound is as chemicals treatment sewage, in generated sludge can contain with O3 catalytic oxidation effect metal or
Metal oxide.In addition, in certain sewage containing this metal or metal oxide with O3 catalytic oxidation effect, in this way
Sewage handled after also can be containing the metal or metal oxide with O3 catalytic oxidation effect in obtained sludge.
These metals or metal oxide with O3 catalytic oxidation effect become a kind of pollutant in above-mentioned sludge, cannot be had
Effect utilizes, and the dewatered sludge of the metal or metal oxide of being capable of O3 catalytic oxidation is contained using this as forming agent, can be with
While ensureing molding effect, catalysis energy of the prepared cellular ozone oxidation catalyst to ozone oxidation is further enhanced
Power makes to be capable of the metal of O3 catalytic oxidation in dewatered sludge or metal oxide gets utilization, avoids the wave of resource
Take.
After obtaining above-mentioned lotion mixture, needs the lotion mixture carrying out extrusion forming processing, obtain cellular embryo
Body.Specifically, extrusion forming of the existing cellular catalyst extrusion equipment realization to the lotion mixture may be used, herein
It is not specifically limited, the lotion mixture can be generally fitted into extrusion equipment, using the uniform extrusion forming of mold, then be led to
It crosses linear cutting equipment and is cut into block-like cellular idiosome, certain extrusion equipment and linear cutting equipment can be setting for integration
Standby, this is also rational.The honeycomb fashion idiosome can be the shapes such as cube, cuboid, specific so that the honeycomb fashion prepared is smelly
Oxygen oxidation catalyst is easy filling in use to be advisable.The honeycomb fashion idiosome is porous structure, and general pitch of holes is 3-10
Millimeter, hole wall thickness are 1-5 millimeters.
Above-mentioned cellular idiosome is dried, calcination process to get to cellular ozone oxidation catalyst, specifically,
Can be 300-600 DEG C of condition in temperature under the conditions of temperature is 60-150 DEG C, after which is dried 5-24 hours
Under, it roasts 2-8 hours.The cellular ozone oxidation catalyst obtained after calcination process has many empty structures, increases the bee
The specific surface area of socket ozone oxidation catalyst.Pass through the specific surface area of cellular ozone oxidation catalyst made from the above method
≥150m2/ g, compression strength ＞ 300N, wear rate≤0.3%W are good to the oxidation catalysis effect of ozone.
It should be noted that above-mentioned crushing, washing, drying, stirring, dehydration and baking operation are behaviour commonly used in the art
Make method, those skilled in the art can not illustrate herein determines according to actual conditions；It is used in above-mentioned preparation method
To the instrument and equipment without specified otherwise be instrument and equipment commonly used in the art, those skilled in the art can be according to practical feelings
Condition is selected, and for example, baking oven may be used and carry out drying and processing, calcination process can carry out in Muffle furnace, herein
It is not specifically limited.
Technical scheme of the present invention is described below in conjunction with specific embodiment, described embodiment is only this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Embodiment 1
Specification by the Shandong safe and sound Environmental Protection Technology Co., Ltd of dragon is LAT-TC, the iron carbon filler that grain size is 1*3 centimetres into
Row crushes, and obtains the powder shaped iron carbon filler that grain size is 0.01 millimeter；
According to mass ratio it is 16 by powder shaped iron carbon filler and forming agent, poly- two propylene dimethyl amine：3：1 ratio is mixed
Close, stirring obtains lotion mixture, dewatered primary deposition sludge in forming agent, humus sludge, digested sludge mass ratio
It is 2：5：3, water content is the 50% of forming agent gross mass；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 5 millimeters, and hole wall thickness is 2 millimeters；
By cellular idiosome under the conditions of 100 DEG C, after 15 hours dry, the Muffle kiln roasting 8 for being 350 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage is 7g/L, and ozone reaction continuous aeration is smelly
Oxygen flow is 0.67L/min, reaction time 30min, pH value 6.8.Sewage source in the present embodiment：It is derived from rich day set of circumstances
Limited liability company of group coal liquifaction sewage treatment project project.The initial water quality index of sewage：CODCrIt (is measured with potassium dichromate method
COD) be 128.3mg/L, coloration be 400 times, turbidity 0.62NTU；Effluent index：CODCrFor 24.6mg/L, color
Degree is 4 times, turbidity 0.32NTU；Water-quality COD after processingCrRemoval rate be 80.8%, the removal rate of coloration is 99.0%, turbid
The removal rate of degree is 48.4%.
Embodiment 2
Discarded iron carbon filler is washed 5 times with clear water, after 24 hours dry in 50 DEG C of baking oven, being ground into grain size is
3 millimeters of iron carbon filler, then crushed, obtain the powder shaped iron carbon filler that grain size is 0.08 millimeter；
According to mass ratio it is 10 by powder shaped iron carbon filler and dewatered chemical sludge, adhesive：7：3 ratio is mixed
It closes, stirring, obtains lotion mixture, the water content of dewatered chemical sludge is 40%, two allyl of poly dimethyl in adhesive
Ammonium chloride, epoxy resin, hydroxyethyl cellulose mass ratio be 1：5：4；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 10 millimeters, and hole wall thickness is 1 millimeter；
By cellular idiosome under the conditions of 80 DEG C, after 24 hours dry, the Muffle kiln roasting 2 for being 600 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage be 11g/L, ozone reaction continuous aeration,
Ozone flow is 0.55L/min, reaction time 30min, pH value 7.4.Sewage source in the present embodiment：It is derived from rich day environment
Group Plc's dyeing and printing sewage advanced treating engineering project.The initial water quality index of sewage：CODCrFor 117.6mg/L,
Coloration is 160 times, turbidity 0.49NTU；Effluent index：CODCrFor 20.6mg/L, coloration is 4 times, turbidity 0.27NTU；Place
Water-quality COD after reasonCrRemoval rate be 82.5%, the removal rate of coloration is 97.5%, and the removal rate of turbidity is 44.9%.
Embodiment 3
Discarded iron carbon filler is washed 3 times with clear water, after 18 hours dry in 85 DEG C of baking oven, being ground into grain size is
4 millimeters of iron carbon filler, then crushed, obtain the powder shaped iron carbon filler that grain size is 0.30 millimeter；
According to mass ratio it is 11 by powder shaped iron carbon filler and forming agent, adhesive：2：4 ratio mixing, stirs to get
Lotion mixture, dewatered chemical sludge in forming agent, humus sludge mass ratio be 1：1, water content is the total matter of forming agent
The 60% of amount, sodium metasilicate in adhesive, polyvinyl alcohol mass ratio be 2：3；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 4 millimeters, and hole wall thickness is 3 millimeters；
By cellular idiosome under the conditions of 120 DEG C, after 5 hours dry, the Muffle kiln roasting 6 for being 450 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage be 14g/L, ozone reaction continuous aeration,
Ozone flow is 0.80L/min, reaction time 25min, pH value 7.7.Sewage source in the present embodiment：It is derived from rich day environment
Group Plc's coal liquifaction sewage treatment project project.The initial water quality index of sewage：CODCrFor 142.6mg/L, color
Degree is 400 times, turbidity 0.63NTU；Effluent index：CODCrFor 15.1mg/L, coloration is 4 times, turbidity 0.32NTU；Processing
Water-quality COD afterwardsCrRemoval rate be 89.4%, the removal rate of coloration is 99.0%, and the removal rate of turbidity is 49.2%.
Embodiment 4
Discarded iron carbon filler is washed 4 times with clear water, after 12 hours dry in 75 DEG C of baking oven, being ground into grain size is
5 millimeters of iron carbon filler, then crushed, obtain the powder shaped iron carbon filler that grain size is 0.10 millimeter；
According to mass ratio it is 12 by powder shaped iron carbon filler and forming agent, adhesive：5：3 ratio mixing, stirring obtain
Lotion mixture, dewatered residual active sludge in forming agent, humus sludge mass ratio be 2：1, water content is forming agent
The 20% of gross mass, polyacrylamide in adhesive, polyethylene, hydroxyethyl cellulose mass ratio be 2：3：1；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 6 millimeters, and hole wall thickness is 4 millimeters；
By cellular idiosome under the conditions of 110 DEG C, after 11 hours dry, the Muffle kiln roasting 5 for being 580 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage be 10g/L, ozone reaction continuous aeration,
Ozone flow is 0.80L/min, reaction time 35min, pH value 7.8.Sewage source in the present embodiment：It is derived from rich day environment
Group Plc's antibiotic medicine advanced treatment of wastewater engineering project.The initial water quality index of sewage：CODCrFor
106.5mg/L, coloration are 320 times, turbidity 0.58NTU；Effluent index：CODCrFor 18.6mg/L, coloration is 4 times, and turbidity is
0.30NTU；Water-quality COD after processingCrRemoval rate be 82.5%, the removal rate of coloration is 98.8%, and the removal rate of turbidity is
48.3%.
Embodiment 5
Discarded iron carbon filler is washed 2 times with clear water, after 5 hours dry in 60 DEG C of baking oven, it is 7 to be ground into grain size
The iron carbon filler of millimeter, then crushed, obtain the powder shaped iron carbon filler that grain size is 0.50 millimeter；
According to mass ratio it is 6 by powder shaped iron carbon filler and dewatered digested sludge, adhesive：2：1 ratio mixing,
Stirring, obtains lotion mixture, and dewatered digested sludge water content is 90%, polyacrylamide in adhesive, lignin
Mass ratio is 3：1；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 8 millimeters, and hole wall thickness is 3 millimeters；
By cellular idiosome under the conditions of 60 DEG C, after 10 hours dry, the Muffle kiln roasting 4 for being 400 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage be 8g/L, ozone reaction continuous aeration, instead
It is 30min, pH value 7.4 between seasonable.Sewage source in the present embodiment：It is derived from Poten Environment Group Co., Ltd.'s antibiosis
Plain medicine advanced treatment of wastewater engineering project.The initial water quality index of sewage：CODCrFor 135.3mg/L, coloration is 320 times, turbidity
For 0.56NTU；Effluent index：CODCrFor 19.5mg/L, coloration is 8 times, turbidity 0.30NTU；Water-quality COD after processingCrGo
Except rate is 85.6%, the removal rate of coloration is 97.5%, and the removal rate of turbidity is 46.4%.
Embodiment 6
Discarded iron carbon filler is washed 5 times with clear water, after 20 hours dry in 90 DEG C of baking oven, being ground into grain size is
10 millimeters of iron carbon filler, then crushed, obtain the powder shaped iron carbon filler that grain size is 0.20 millimeter；
According to mass ratio it is 4 by powder shaped iron carbon filler and forming agent, adhesive：3：1 ratio mixing, stirring obtain
Lotion mixture, dewatered primary deposition sludge in forming agent, residual active sludge mass ratio be 4：1, water content be at
The 80% of type agent gross mass, polyethylene in adhesive, poly- two propylene dimethyl amine mass ratio be 1：2；
Lotion mixture is fitted into extrusion equipment, after mold uniformly squeezes, wire cutting obtains cellular idiosome, bee
Socket idiosome pitch of holes is 3 millimeters, and hole wall thickness is 5 millimeters；
By cellular idiosome under the conditions of 150 DEG C, after 18 hours dry, the Muffle kiln roasting 8 for being 300 DEG C in temperature is small
When, obtain cellular ozone oxidation catalyst.
Catalytic ozonation is tested：Cellular ozone oxidation catalyst dosage be 11g/L, ozone reaction continuous aeration,
Ozone flow is 0.74L/min, reaction time 30min, pH value 7.4.Sewage source in the present embodiment：It is derived from rich day environment
Group Plc's dyeing and printing sewage advanced treating engineering project.The initial water quality index of sewage：CODCrFor 108.1mg/L,
Coloration is 160 times, turbidity 0.47NTU；Effluent index：CODCrFor 17.9mg/L, coloration is 4 times, turbidity 0.27NTU；Place
Water-quality COD after reasonCrRemoval rate be 83.4%, the removal rate of coloration is 97.5%, and the removal rate of turbidity is 42.5%.
Comparative example 1
Ozone oxidation catalyst selects ferric oxide powder (the plentiful and substantial Chemical Co., Ltd. in Changzhou, mesh number：600 mesh, type
Number：101).
Catalytic ozonation is tested：Ozone oxidation catalyst dosage is 11g/L, ozone reaction continuous aeration, flow of ozone
Amount is 0.74L/min, reaction time 40min, pH value 7.4.Wastewater source in the present embodiment：It is derived from Bo Tian environment group stock
Part Co., Ltd dyeing waste water advanced treating engineering project.The initial water quality index of waste water：CODCrFor 108.1mg/L, coloration is
160 times, turbidity 0.47NTU；Effluent index：CODCrFor 62.5mg/L, coloration is 8 times, turbidity 0.33NTU；Water after processing
Matter CODCrRemoval rate be 42.2%, the removal rate of coloration is 95.0%, and the removal rate of turbidity is 29.8%.
Comparative example 2
Ozone oxidation catalyst selects copper oxide (Cangzhou City Li Fa commerce and trade Co., Ltd, product hierarchy：It is ultra-fine, model/rule
Lattice：Technical grade 98%, content：98%).
Catalytic ozonation is tested：Ozone oxidation catalyst dosage is 11g/L, ozone reaction continuous aeration, flow of ozone
Amount is 0.74L/min, reaction time 50min, pH value 7.4.Wastewater source in the present embodiment：It is derived from Bo Tian environment group stock
Part Co., Ltd dyeing waste water advanced treating engineering project.The initial water quality index of waste water：CODCrFor 108.1mg/L, coloration is
160 times, turbidity 0.47NTU；Effluent index：CODCrFor 64.6mg/L, coloration is 8 times, turbidity 0.34NTU；Water after processing
Matter CODCrRemoval rate be 40.2%, the removal rate of coloration is 95.0%, and the removal rate of turbidity is 27.6%.
It is dirty by above-described embodiment 1-6 as it can be seen that using the cellular ozone oxidation catalyst treated sewage prepared by the present invention
1g COD are reduced in water to need to consume 1.3-2.5g ozone, the sewage that processing COD is 100-150mg/L, reaction time 5-
30min.By above-mentioned comparative example 1 and 2 as it can be seen that 1g COD need to consume 2.0- in catalysis ozone technology reduction sewage in the prior art
4.0g ozone, the sewage that processing COD is 100-150mg/L, reaction time need 30-60min.It can be seen that with prior art phase
Than, using the cellular ozone oxidation catalyst prepared by the present invention, to ozone utilization ratio 90% or more, reaction rate
Soon, also there is removal well to imitate for coloration and turbidity to the removal rate of the COD in sewage 80% or more, while to sewage
Fruit.
A kind of preparation method of cellular ozone oxidation catalyst provided in an embodiment of the present invention is simple to operation, using useless
The iron carbon filler and dewatered sludge abandoned further reduced manufacturing cost, realize the recycling of resource as raw material is prepared, and fit
Close industrialized production.The cellular ozone oxidation catalyst prepared using the preparation method, it is active due to containing in iron carbon filler
Charcoal makes have a large amount of pore passage structure in cellular ozone oxidation catalyst obtained, large specific surface area, excellent catalytic effect, separately
On the one hand, since iron carbon filler has the iron carbon structure that iron and metallic catalyst and charcoal contain formation framework formula together, iron, gold
Metal catalyst and charcoal are integrated, are not readily separated, catalyst activity component stripping quantity substantially reduces, and does not easily cause secondary pollution.
Above to a kind of cellular preparation method of ozone oxidation catalyst provided by the present invention and its catalysis of preparation
Agent is described in detail.Principle and implementation of the present invention are described for specific embodiment used herein, with
The explanation of upper embodiment is merely used to help understand the method and its central idea of the present invention.It should be pointed out that for this field
For those of ordinary skill, without departing from the principle of the present invention, can with several improvements and modifications are made to the present invention,
These improvement and modification also fall into the protection of the claims in the present invention.
Claims (10)
1. a kind of preparation method of honeycomb fashion ozone oxidation catalyst, which is characterized in that including：
Iron carbon filler is crushed, powder shaped iron carbon filler is obtained；The iron carbon filler is the iron carbon filler discarded；
According to mass ratio it is (6-16) by the powder shaped iron carbon filler and forming agent, adhesive：(2-12)：The ratio of (1-4)
Mixing, stirring, obtains lotion mixture；
The lotion mixture is subjected to extrusion forming processing, obtains cellular idiosome；
The cellular idiosome is dried, calcination process obtains cellular ozone oxidation catalyst.
2. preparation method as described in claim 1, which is characterized in that it is described by iron carbon filler crush including：It will be described
It is dried after discarded iron carbon filler washing, is first ground into grain size and is 3-10 millimeters of iron carbon filler, then be crushed into powder
Body shape iron carbon filler.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the grain size of the powder shaped iron carbon filler is 0.01-
0.50 millimeter.
4. preparation method as claimed in claim 1 or 2, which is characterized in that the forming agent is dewatered sludge, and the dehydration is dirty
Mud drum includes：In primary deposition sludge, residual active sludge, humus sludge, digested sludge, chemical sludge by dehydration
One or more, the water content of the dewatered sludge are the 20%-90% of the dewatered sludge gross mass.
5. preparation method as claimed in claim 4, which is characterized in that the dewatered sludge, which contains, is capable of O3 catalytic oxidation
Metal or metal oxide.
6. preparation method as claimed in claim 1 or 2, which is characterized in that described adhesive includes：Sodium metasilicate, epoxy resin,
Polyvinyl alcohol, lignin, polyacrylamide, poly- two propylene dimethyl amine, polydimethyl diallyl ammonium chloride, polyethylene, hydroxyl
It is one or more in ethyl cellulose.
7. preparation method as claimed in claim 1 or 2, which is characterized in that the honeycomb fashion idiosome is porous structure, pitch of holes
It it is 3-10 millimeters, hole wall thickness is 1-5 millimeters.
8. preparation method as claimed in claim 1 or 2, which is characterized in that the drying is specially：It it is 60-150 DEG C in temperature
Under the conditions of, it is 5-24 hours dry；The calcination process is specially：Under the conditions of temperature is 300-600 DEG C, roast 2-8 hours.
9. the cellular ozone oxidation catalyst prepared by the preparation method described in any one of claim 1-8.
10. honeycomb fashion ozone oxidation catalyst as claimed in claim 9, which is characterized in that the honeycomb fashion ozone oxidation is urged
Specific surface area >=150m of agent2/ g, compression strength ＞ 300N, wear rate≤0.3%W.
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| CN109513439A (en) * | 2018-06-13 | 2019-03-26 | 江苏湖大化工科技有限公司 | A kind of catalyst for waste water debirs advanced oxidation degradation |
| CN108558146A (en) * | 2018-06-13 | 2018-09-21 | 江苏湖大化工科技有限公司 | Process and device associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater |
| CN108947099A (en) * | 2018-06-13 | 2018-12-07 | 江苏湖大化工科技有限公司 | A kind of advanced oxidation processes treatment process device and method of the waste water containing sodium phenolate |
| CN108558084B (en) * | 2018-06-13 | 2024-01-23 | 江苏湖大化工科技有限公司 | Treatment method and device for electrolytic catalysis coupling advanced oxidation of organic matters in high-salt wastewater |
| CN111499094B (en) * | 2020-04-13 | 2023-03-17 | 南京卓越环保科技有限公司 | Harmless treatment method of high-concentration pyridinol sodium acid water |
| CN112408578B (en) * | 2020-11-26 | 2022-11-15 | 上海绿强新材料有限公司 | Catalytic ozone oxidation honeycomb filler and preparation and printing and dyeing wastewater advanced treatment method |
| CN113171783B (en) * | 2021-04-21 | 2023-03-21 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
| CN114471603A (en) * | 2022-01-24 | 2022-05-13 | 上海中耀环保实业有限公司 | Non-supported ozone catalyst and use method thereof |
| CN114620811A (en) * | 2022-02-28 | 2022-06-14 | 蔡同春 | Quantum migration multidimensional electrolytic catalysis method and equipment |
| CN115301295B (en) * | 2022-09-14 | 2023-08-25 | 广东卓信环境科技股份有限公司 | Honeycomb catalyst for catalytic oxidation of ozone and preparation method and application thereof |
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