CN113289603B - Calcium-based catalyst for catalyzing ozone oxidation and preparation method and application thereof - Google Patents
Calcium-based catalyst for catalyzing ozone oxidation and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 61
- 230000003647 oxidation Effects 0.000 title claims abstract description 59
- 239000011575 calcium Substances 0.000 title claims abstract description 53
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 102000002322 Egg Proteins Human genes 0.000 claims description 6
- 108010000912 Egg Proteins Proteins 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 210000003278 egg shell Anatomy 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 238000006385 ozonation reaction Methods 0.000 claims description 4
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- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 3
- 239000010815 organic waste Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
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- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
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- 239000007789 gas Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
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- 229910000367 silver sulfate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 229910003872 O—Si Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/396—
-
- 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
- C02F1/725—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
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a calcium-based catalyst for catalyzing ozone oxidation, and a preparation method and application thereof. The calcium-based catalyst for catalyzing ozone oxidation has a core-shell structure, takes CaO as a core and takes porous SiO as a core 2 Is a shell. Adding a CaO precursor into deionized water, and stirring to obtain a suspension A; by means of SiO 2 Preparing silica sol B from the precursor; adding the suspension A into the silica sol B, and stirring to obtain a suspension C; aging the suspension C, and filtering to obtain a precipitate D; washing and drying the precipitate D to obtain a catalyst precursor E; and drying and roasting the catalyst precursor E to obtain the calcium-based catalyst for catalyzing the ozone oxidation. The calcium-based catalyst has the characteristics of high catalytic activity, long catalytic life, environmental friendliness, no heavy metal pollution and easiness in preparation.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a calcium-based catalyst for catalyzing ozone oxidation, and a preparation method and application thereof.
Background
Water is a necessary resource for living and human development, but water pollution seriously threatens the ecological environment and human health. According to the statistical data of the Chinese environmental condition bulletin, the pollution situation of seven water systems in China is still severe. The discharge of industrial organic wastewater is a main pollution source, wherein industrial wastewater from industries such as papermaking printing, petrochemical industry, metallurgical electroplating and the like has the characteristics of complex pollution components, high toxic content, high COD (chemical oxygen demand), strong acidity or alkalinity, great harm, difficult degradation and the like, causes serious pollution to soil, water and atmosphere, and can effectively reduce the discharge of industrial organic wastewater through source degradation treatment of the organic wastewater.
Advanced oxidation technology is a novel technology that realizes degrading organic waste water through the strong oxidizing property of hydroxyl radical, and the oxidation potential of hydroxyl radical is much higher than ordinary oxidant (such as chlorine, hydrogen peroxide and ozone), and the oxidizing power is very strong, can be with the organic matter direct oxidation of macromolecule carbon dioxide and water to reaction process green, environmental protection can not cause the pollution to the environment, is applied to the waste water treatment in-process by more and more enterprises gradually.
Ozone is a gas with strong oxidizing property, the oxidizing ability is second to fluorine in natural elements, the ozone is used for degrading organic wastewater, and the ozone has the characteristics of rapid reaction, small equipment size, low equipment cost, easy decomposition of residual ozone into oxygen and no secondary pollution. However, when the existing catalyst is used for catalyzing ozone oxidation and degrading organic wastewater, the problem that heavy metal elements overflow and enter water to cause secondary water pollution is solved, and the existing catalyst has high catalytic oxidation selectivity on target organic compounds.
Chinese patent CN 108543534A discloses a catalyst for catalyzing ozone oxidation and a preparation method thereof, and the catalyst particle carrier is ZrO doped with carbon and cerium 2 The doping amount of carbon is 0.5% -2%, the doping amount of cerium is 6% -17%, and the active components are Ru and Ce alternately loaded on the carrier in a layered manner, wherein the loading amount of Ru is 0.05% -0.1%, and the loading amount of Ce is 1% -5%. In the catalytic ozonation process, metal ion cerium can enter a water body due to the overflow of effective components, and then the water body can be causedSecondary pollution of (2).
Chinese patent CN 109908934 a discloses a catalyst for catalytic oxidation reaction of ozone and a preparation method thereof, the catalyst comprises a composite carrier and an active metal component, noble metal is used as the active metal component, and the composite carrier comprises activated carbon and basic carbonate. The preparation method comprises the steps of mixing activated carbon and a soluble organic salt solution, introducing a carbonate solution or an alkaline solution into a material A after uniformly mixing, and obtaining a material B, and carrying out solid-liquid separation, drying and roasting to obtain a material C; and mixing the material C with water, introducing carbon dioxide gas for reaction, cooling, performing solid-liquid separation, drying and roasting a solid phase obtained by separation to obtain a composite carrier material, finally impregnating active metal and optional auxiliary agent components, and drying and roasting to obtain the catalyst. Although the noble metal catalyst in the patent has good stability and long service life, and also has a large number of oxygen adsorption sites, hydrocarbon adsorption and oxygen activation can be rapidly carried out when surface reaction is carried out, the noble metal catalyst is high in cost and difficult to recover, heavy metal ions are dissolved into a solution to cause secondary pollution, and noble metal elements do not play a role of an active center in experiments in most cases, so that the development of the noble metal catalyst in the aspect of catalyzing ozone oxidation to degrade organic pollutants is limited.
At present, the calcium-based catalyst for catalyzing ozone oxidation, which has high catalytic activity, is environment-friendly and is easy to prepare, is urgently needed to be provided.
Disclosure of Invention
The invention aims to provide a calcium-based catalyst for catalyzing ozone oxidation, which has the characteristics of higher catalytic activity, longer catalytic life, environmental friendliness, no heavy metal pollution and easiness in preparation; the invention also provides a preparation method and application of the calcium-based catalyst for catalyzing ozone oxidation.
The calcium-based catalyst for catalyzing ozone oxidation has a core-shell structure, takes CaO as a core and takes porous SiO as a porous material 2 Is a shell.
The mass of the CaO is porous SiO 2 10-30% of the mass.
The preparation method of the calcium-based catalyst for catalyzing ozone oxidation comprises the following steps:
(1) adding a CaO precursor into deionized water, and stirring to obtain a suspension A;
(2) by means of SiO 2 Preparing silica sol B from the precursor;
(3) adding the suspension A into the silica sol B, and stirring to obtain a suspension C; aging the suspension C, and filtering to obtain a precipitate D;
(4) washing and drying the precipitate D to obtain a catalyst precursor E;
(5) and drying and roasting the catalyst precursor E to obtain the calcium-based catalyst for catalyzing the ozone oxidation.
The CaO precursor in the step (1) is one of calcium carbonate, calcium oxalate, eggshell or shell, the mesh number of the eggshell is 400 meshes, and the mesh number of the shell is 400 meshes.
The proportion of the CaO precursor to the deionized water in the step (1) is 4-8: 20-50, wherein the CaO precursor is calculated by g, and the deionized water is calculated by ml.
SiO as described in step (2) 2 The precursor is sodium silicate or ethyl orthosilicate.
The preparation method of the silica sol B in the step (2) is to disperse sodium silicate in deionized water and add NH 4 And (3) reacting the Cl solid to prepare silica sol B or dissolving tetraethoxysilane in an ethanol solution, and then adding the solution into a mixed solution of concentrated ammonia water, ethanol and deionized water to react to prepare the silica sol B.
The stirring time in the step (3) is 60-240min, and the aging time is 4-24 h.
The drying temperature in the step (4) is 60-120 ℃, and the drying time is 4-8 h.
The washing in the step (4) is washing with deionized water.
The drying temperature in the step (5) is 60-120 ℃, and the drying time is 4-8 h.
The roasting temperature in the step (5) is 500-1000 ℃, and the roasting time is 2-8 h.
The application of the calcium-based catalyst for catalyzing ozone oxidation is used for treating organic wastewater, and the method comprises the following steps:
adding a calcium-based catalyst for catalyzing ozone oxidation into the organic wastewater, and introducing mixed gas of ozone and air for reaction to obtain the catalyst.
The organic wastewater is one or more of alcohol wastewater, aldehyde wastewater, carboxylic acid wastewater, amine wastewater or phenol wastewater.
The proportion of the calcium-based catalyst for catalyzing ozone oxidation to the organic wastewater is 1.0-1.5: 1, wherein the calcium-based catalyst for catalyzing ozone oxidation is calculated by g, and the organic wastewater is calculated by L.
The volume ratio of the ozone to the air is 1: 49-61.
The reaction time is 1-2 h.
According to the invention, the silica sol and the CaO precursor are fully mixed, the silica sol is changed into a gel state along with the aging, the silica sol is coated around the CaO precursor, and CO generated by decomposition of the CaO precursor through high-temperature roasting 2 Overflowing to form pores on the CaO-coated silicon oxide layer, and preparing the final catalyst with CaO as core and porous SiO 2 Forming a core-shell structure; and due to the generation of Ca-O-Si bonds between the calcium oxide and the silicon dioxide, the prepared catalyst is more stable, and the diffusion of effective components in a wastewater solution is prevented.
In the invention, one of calcium carbonate, calcium oxalate, eggshell or shell can be used as a CaO precursor and also can be used as a template agent.
The invention aims to design a calcium-based catalyst for catalyzing ozone oxidation to treat organic wastewater, which can effectively promote the generation of active free radicals in the ozone oxidation reaction, catalyze ozone oxidation to degrade various organic compounds, and can maximally degrade the organic compounds in the wastewater. Porous SiO in the treatment of organic waste water 2 Organic matters and O in the organic wastewater 3 Adsorbed on the catalyst, CaO as the main active substance catalyzes O 3 And H 2 The O reaction generates free radicals to degrade the adsorbed organic matter. During the treatment, due to the calcium oxide and the di-oxide in the catalystThe Ca-O-Si bond between the silicon oxide is generated, so that the calcium oxide and the silicon dioxide have strong enough interaction, the leaching of an active phase in an aqueous solution can be effectively prevented, the service life of the catalyst is prolonged, and the influence of the addition of calcium ions on the hardness of a water body is reduced.
The invention has the following beneficial effects:
the calcium-based catalyst for catalyzing ozone oxidation provided by the invention takes calcium oxide as a main substance, the raw materials are cheap and easy to obtain, the environment is friendly, carbon and hydrogen elements in a catalyst precursor are removed in the form of carbon dioxide and water by coating silicon dioxide and high-temperature roasting, wherein carbon dioxide gas overflows to form a pore channel, the surface area of the catalyst is increased, more active sites are provided for the catalyst, and therefore, the removal rate of organic matters in wastewater is improved, and the removal rate of COD is more than 90%; and the service life of the catalyst is prolonged due to the generation of Ca-O-Si bonds between calcium oxide and silicon dioxide in the catalyst.
Drawings
FIG. 1 is a schematic diagram of the catalytic mechanism of the calcium-based catalyst for catalyzing ozone oxidation prepared according to the present invention.
Fig. 2 is a TEM image of the calcium-based catalyst for catalyzing ozone oxidation prepared in example 1.
Fig. 3 is an infrared spectrum of the calcium-based catalyst for catalyzing ozone oxidation prepared in example 1.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The preparation method of the calcium-based catalyst for catalyzing ozone oxidation comprises the following steps:
(1) weighing 7.69g of CaCO 3 Dispersing in 50ml of deionized water, and uniformly stirring to prepare a suspension A;
(2) 35g of sodium silicate was weighed out and dispersed in 100ml of deionized water, and 8.91g of NH was added 4 Performing solid reaction on Cl to prepare silica sol B;
(3) adding the suspension A into the silica sol B, and stirring for 60min to obtain a suspension C; standing and aging the suspension C for 4h at room temperature, and filtering to obtain a precipitate D;
(4) washing the precipitate D with deionized water, and drying at 60 ℃ for 8h to obtain a catalyst precursor E;
(5) and drying the obtained catalyst precursor E at 80 ℃ for 4h, and roasting at 1000 ℃ for 2h to obtain the calcium-based catalyst for catalyzing ozone oxidation.
A TEM image of the calcium-based catalyst used to catalyze ozone oxidation is shown in figure 2.
The infrared spectrum of the calcium-based catalyst used to catalyze the ozonation is shown in fig. 3.
In the infrared spectrum, pure SiO 2 1050cm in microsphere -1 The characteristic peak of the catalyst is attributed to Si-O-Si bond, and 991cm in the prepared calcium-based catalyst -1 The peak at (A) is attributed to newly formed Si-O-Ca bond, which is also responsible for the long service life of the prepared catalyst, while 870cm -1 The peak at (A) was ascribed to the peak of the CaO stretching vibration, and the peak of the Si-O bond was shifted to 942cm -1 To (3).
The application of the calcium-based catalyst for catalyzing ozone oxidation is as follows:
pouring 300ml of prepared 210g/L simulated phenol wastewater into a reactor, weighing 0.5g of the calcium-based catalyst for catalyzing ozone oxidation, putting the calcium-based catalyst into the wastewater in the reactor, and introducing mixed gas of ozone and air at a flow rate of 1.0L/min, wherein the volume ratio of the ozone to the air is 1: 55, reacting for one hour, sampling every 10min, filtering with a 0.22 μm filter membrane after sampling, digesting with an oxidant prepared from silver sulfate and concentrated sulfuric acid, measuring the COD value with a chemical oxygen demand measuring instrument, and measuring the result: the initial COD is 510mg/L, after the ozone catalytic oxidation degradation, the COD is reduced to 45.54mg/L, and the removal rate of the COD is 91.07%.
And (3) filtering and collecting the catalyst after the reaction is finished, drying, continuing to perform the experimental operation process, and repeating the experimental reaction for 3 times to explore the relationship between the removal rate of COD and the use times of the catalyst, wherein the experimental result is shown in Table 1.
Wherein, the COD removal rate calculation method comprises
TABLE 1 relationship table between COD removal rate and number of times of catalyst use in example 1
| Number of times of use | 1 | 2 | 3 | 4 |
| COD removal rate | 91.07％ | 87.45％ | 83.02％ | 81％ |
As can be seen from table 1, the activity of the catalyst still has 81% removal efficiency after 4 times of reuse, and this result also proves that the synthesized calcium-based catalyst can be reused many times without affecting the catalytic activity thereof, and has higher stability.
Example 2
The preparation method of the calcium-based catalyst for catalyzing ozone oxidation comprises the following steps:
(1) weighing 4.00g of CaC 2 O 4 Dispersing in 40ml of deionized water, and uniformly stirring to obtain a suspension A;
(2) 10g of sodium silicate was weighed and dispersed in 100ml of deionized water, and 8.91g of NH was added 4 ClCarrying out solid reaction to prepare silica sol B;
(3) adding the suspension A into the silica sol B, and stirring for 240min to obtain a suspension C; standing and aging the suspension C for 24h at room temperature, and filtering to obtain a precipitate D;
(4) washing the precipitate D with deionized water, and drying at 120 ℃ for 4h to obtain a catalyst precursor E;
(5) and drying the obtained catalyst precursor E at 60 ℃ for 6h, and roasting at 800 ℃ for 6h to obtain the calcium-based catalyst for catalyzing ozone oxidation.
The application of the calcium-based catalyst for catalyzing ozone oxidation is as follows:
pouring 300ml of prepared 210g/L simulated norfloxacin wastewater into a reactor, weighing 0.5g of the calcium-based catalyst for catalyzing ozone oxidation into the wastewater in the reactor, and introducing mixed gas of ozone and air at a flow rate of 1.0L/min, wherein the volume ratio of the ozone to the air is 1: 50, reacting for one hour, sampling every 10min, filtering with a 0.22 μm filter membrane after sampling, digesting with an oxidant prepared from silver sulfate and concentrated sulfuric acid, measuring the COD value by a chemical oxygen demand measuring instrument, and measuring the result: the initial COD is 560mg/L, after ozone catalytic oxidation degradation, the COD is reduced to 25.5mg/L, and the removal rate of the COD is 95%.
Example 3
The preparation method of the calcium-based catalyst for catalyzing ozone oxidation comprises the following steps:
(1) weighing 5g of eggshell powder (sieved by a 400-mesh sieve) and dispersing the eggshell powder in 45ml of deionized water, and uniformly stirring to prepare a suspension A;
(2) measuring 4.5ml of tetraethoxysilane, dissolving the tetraethoxysilane in 45.5ml of ethanol solution, and quickly adding the tetraethoxysilane into a mixed solution prepared from 9ml of strong ammonia water, 16.25ml of ethanol and 24.75ml of deionized water for reaction to prepare silica sol B;
(3) adding the suspension A into the silica sol B, and stirring for 100min to obtain a suspension C; standing and aging the suspension C for 12h at room temperature, and filtering to obtain a precipitate D;
(4) washing the precipitate D with deionized water, and drying at 80 ℃ for 6h to obtain a catalyst precursor E;
(5) and drying the obtained catalyst precursor E at 120 ℃ for 4h, and roasting at 700 ℃ for 8h to obtain the calcium-based catalyst for catalyzing ozone oxidation.
The application of the calcium-based catalyst for catalyzing ozone oxidation is as follows:
pouring 300ml of prepared 210g/L simulated aniline wastewater into a reactor, weighing 0.5g of the calcium-based catalyst for catalyzing ozone oxidation, putting the calcium-based catalyst into the wastewater in the reactor, and introducing mixed gas of ozone and air at a flow rate of 1.0L/min, wherein the volume ratio of the ozone to the air is 1: 60, reacting for one hour, sampling every 10min, filtering with a 0.22 μm filter membrane after sampling, digesting with an oxidant prepared from silver sulfate and concentrated sulfuric acid, measuring the COD value with a chemical oxygen demand measuring instrument, and measuring the result: the initial COD is 565mg/L, after ozone catalytic oxidation degradation, the COD is reduced to 40.8mg/L, and the removal rate of the COD is 92%.
Comparative example 1
(1) Weighing 23.5906g Mg (NO) 3 ) 2 And dissolved in 100ml of deionized water, and the mixture is stirred uniformly to prepare a solution A.
(2) Weighing 9.9769g/L Co (NO) 3 ) 2 Dissolve in 1L of deionized water to obtain solution B. 52ml of the solution B was measured and added to the solution A, and stirred for 15min to obtain a mixed solution C.
(3) Weighing 9.7511gNa 2 CO 3 Dissolving in 100ml deionized water, stirring well to obtain solution D, pouring solution D into mixed solution C, and stirring for 45min to obtain suspension E.
(4) And (3) aging the suspension E for 3h, carrying out suction filtration, washing with deionized water for several times, drying at 90 ℃ for 4h to obtain a precursor, grinding the precursor, and roasting at 500 ℃ for 4h in a muffle furnace at the temperature rise rate of 5 ℃/min to obtain the active catalyst.
300ml of prepared 210mg/L simulated phenol wastewater is put into a three-neck flask, 0.5g of the prepared catalyst is weighed and put into the simulated wastewater, the flow rate of the mixed gas of ozone and air is 1.0L/min, and the volume ratio of the ozone to the air is 1: 55, the reaction is carried out for 1h, samples are taken every 10min, after sampling, the samples are filtered by a filter membrane of 0.22um, digested by an oxidant and the COD value of the samples is measured by a chemical oxygen demand measuring instrument. The initial COD is 510mg/L, after the ozone catalytic oxidation degradation, the COD is reduced to 178.5mg/L, and the removal rate of the COD is 65%.
Comparative example 2
(1) 9.04g MgCO was weighed 3 Dispersing in 50ml of deionized water, and uniformly stirring to obtain a suspension A;
(2) 35g of sodium silicate was weighed out and dispersed in 100ml of deionized water, and 8.91g of NH was added 4 Reacting Cl solid to prepare silica sol B;
(3) adding the suspension A into the silica sol B, and stirring for 60min to obtain a suspension C; standing and aging the suspension C for 4h at room temperature, and filtering to obtain a precipitate D;
(4) washing the precipitate D with deionized water, and drying at 60 ℃ for 8h to obtain a catalyst precursor E;
(5) and drying the obtained catalyst precursor E at 80 ℃ for 4h, and roasting at 1000 ℃ for 2h to obtain the magnesium-based catalyst for catalyzing ozone oxidation.
The application of the magnesium-based catalyst for catalyzing ozone oxidation is as follows:
pouring 300ml of prepared 210g/L simulated phenol wastewater into a reactor, weighing 0.5g of the magnesium-based catalyst for catalyzing ozone oxidation, putting the magnesium-based catalyst into the wastewater in the reactor, and introducing mixed gas of ozone and air at a flow rate of 1.0L/min, wherein the volume ratio of the ozone to the air is 1: 55, reacting for one hour, sampling every 10min, filtering with a filter membrane of 0.22 μm after sampling, digesting with an oxidizing agent prepared from silver sulfate and concentrated sulfuric acid, measuring the COD value with a chemical oxygen demand measuring instrument, and measuring the result: the initial COD is 510mg/L, after the ozone catalytic oxidation degradation, the COD is reduced to 168.2mg/L, and the COD removal rate is 67%.
And (3) filtering and collecting the catalyst after the reaction is finished, drying, continuing to perform the experimental operation process, and repeating the experimental reaction for 3 times to explore the relationship between the removal rate of COD and the using times of the catalyst, wherein the experimental result is shown in Table 2.
TABLE 2 relationship table between COD removal rate and catalyst usage number in example 2
| Number of times of use | 1 | 2 | 3 | 4 |
| COD removal rate | 67％ | 40.05％ | 38.75％ | 35.51％ |
As can be seen from table 2, the activity of the catalyst is greatly reduced after 4 times of reuse, and this result also demonstrates that the reuse of the synthesized magnesium-based catalyst affects its catalytic activity, and the stability is inferior compared to the synthesized calcium-based catalyst of the present invention.
Claims (8)
1. A calcium-based catalyst for catalyzing ozone oxidation is characterized in that the structure of the catalyst is a core-shell structure, CaO is taken as a core, and porous SiO is taken as 2 Is a shell;
the preparation method of the calcium-based catalyst for catalyzing ozone oxidation comprises the following steps:
(1) adding a CaO precursor into deionized water, and stirring to obtain a suspension A;
(2) by means of SiO 2 Preparing silica sol B from the precursor;
(3) adding the suspension A into the silica sol B, and stirring to obtain a suspension C; aging the suspension C, and filtering to obtain a precipitate D;
(4) washing and drying the precipitate D to obtain a catalyst precursor E;
(5) drying and roasting the catalyst precursor E to obtain a calcium-based catalyst for catalyzing ozone oxidation;
the CaO precursor in the step (1) is one of calcium carbonate, calcium oxalate, eggshell or shell.
2. The calcium-based catalyst for catalyzing oxidation of ozone as set forth in claim 1, wherein said CaO is in the form of porous SiO 2 10-30% of the mass.
3. The calcium-based catalyst for catalyzing ozonation according to claim 1, wherein the ratio of the CaO precursor to the deionized water in the step (1) is 4-8: 20-50, wherein the CaO precursor is calculated by g, and the deionized water is calculated by ml.
4. The calcium-based catalyst for catalyzing oxidation of ozone as claimed in claim 1, wherein the SiO in step (2) 2 The precursor is sodium silicate or ethyl orthosilicate.
5. The calcium-based catalyst for catalyzing ozonation according to claim 1, wherein the stirring time in step (3) is 60 to 240min, and the aging time is 4 to 24 hours.
6. The calcium-based catalyst for catalyzing oxidation by ozone as set forth in claim 1, wherein the drying temperature in the step (4) is 60 to 120 ℃ and the drying time is 4 to 8 hours.
7. The calcium-based catalyst for catalyzing oxidation of ozone as claimed in claim 1, wherein the drying temperature in step (5) is 60-120 ℃, the drying time is 4-8h, the calcination temperature is 500-1000 ℃, and the calcination time is 2-8 h.
8. Use of a calcium-based catalyst for catalysing the oxidation of ozone as claimed in any one of claims 1 to 7, for the treatment of organic waste water, comprising the steps of:
adding a calcium-based catalyst for catalyzing ozone oxidation into the organic wastewater, and introducing mixed gas of ozone and air for reaction to obtain the catalyst.
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