CN114797887A - Ozone catalyst and preparation method and application thereof - Google Patents

Ozone catalyst and preparation method and application thereof Download PDF

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Publication number
CN114797887A
CN114797887A CN202110079178.XA CN202110079178A CN114797887A CN 114797887 A CN114797887 A CN 114797887A CN 202110079178 A CN202110079178 A CN 202110079178A CN 114797887 A CN114797887 A CN 114797887A
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parts
ozone
catalyst
ozone catalyst
water
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不公告发明人
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Aws Environment Technologies Ltd
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • 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
    • 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
    • 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
    • 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
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Abstract

The invention discloses an ozone catalyst and a preparation method and application thereof, belonging to the field of water pollution purification. The ozone catalyst comprises the following components in parts by weight: 10-20 parts of manganese ferrite, 40-65 parts of hollow fly ash floating beads, 10-15 parts of clay, 10-15 parts of glass powder and 2-7 parts of sodium alginate. The ozone catalyst prepared by the invention can effectively remove organic pollutants in wastewater and reduce the leaching of metal ions; meanwhile, the apparent density of the product is close to that of water, the stability is good, and the strength is high. The preparation method of the ozone catalyst is simple and easy to operate.

Description

Ozone catalyst and preparation method and application thereof
Technical Field
The invention relates to an ozone catalyst and a preparation method and application thereof, belonging to the field of water pollution purification.
Background
Ozone is a common oxidant, and can be converted into nontoxic oxygen after reacting with reducing substances, so that secondary pollution is avoided. Therefore, the ozone process is widely applied to the fields of organic wastewater treatment and tap water pretreatment. Among them, the catalytic oxidation process by ozone is the most efficient. At present, a reaction tank applied to ozone catalytic oxidation engineering is generally in a fixed bed form, and a used catalyst is mainly high-density metal pellet or a carrier type catalyst. Ozone is easy to form a channel flow in the fixed bed, only a small amount of catalyst can be contacted with ozone, and the catalytic effect of the fixed bed is not obvious. Meanwhile, in order to ensure that the wastewater is fully contacted with the catalytic bed, the filling rate of the catalyst is usually more than 95%, so that the engineering construction cost is greatly increased. On the other hand, the fixed bed catalyst is easy to scale or harden, the activity of the catalyst is reduced, and the replacement and maintenance difficulty is high due to the overlarge density of the catalyst. Therefore, the development of a proper-density, moderate-size, high-efficiency ozone catalyst for constructing a fluidized bed or floating bed reaction tank is one of the important means for improving the ozone catalytic water treatment process.
Patent CN102151567A proposes a catalyst for decomposing organic pollutants in water by ozone and a method for treating sewage by catalyzing ozone. The catalyst is spinel ferrite MnFe 2 O 4 ，CoFe 2 O 4 ，ZnFe 2 O 4 And the spinel ferrite catalyst has good ozone catalytic activity and can be magnetically recycled, but the powder or the supported catalyst has higher density, is not suitable for being applied to a suspended fluidized bed and limits the application range of the suspended fluidized bed. Patent CN106955686B provides a preparation and application method of a diatomite-supported multi-metal ozone catalyst. The catalyst takes large-particle diatomite as a carrier, active silicate is generated on the surface of the diatomite through acid-base corrosion, subsequently-impregnated active metal can perform ion exchange reaction on the diatomite, the roasted active metal can be stably loaded on the carrier, and the diatomite is beneficial to reducing leaching of metal ions. But the catalyst has higher density, is only suitable for a fixed bed and is not easy to form a more efficient ozone fluidized bed. Patent CN106391128A discloses a preparation method of a supported ozone catalyst for treating steel wastewater. The catalyst takes sodium alginate as a carrier, manganese, nickel, silver, cerium and the like as active components of the catalyst, and CaCl 2 The components are used as a cross-linking agent, and gel balls are formed after the components are mixed and cross-linked to obtain the finished catalyst. However, the catalyst still has disadvantages: (1) the transition metal is still in a simple combination form of multiple metal substances, and the active metal is easy to leach out and is easy to cause secondary pollution to water. (2) The sodium alginate component which plays a role of bonding or skeleton is organic matter, and in the long-term operation process of the fluidized bed, the ozone with oxidability can react with the alginic acidSodium gradually degrades and the catalyst risks total pulverization. Patent CN106944027B discloses a preparation method and an application method of a millimeter-sized mesoporous ozone catalyst, which uses sodium alginate as a template to prepare a millimeter-sized mesoporous titanium-zirconium composite pellet, and then compounds cerium and titanium-zirconium composite by an impregnation method. Although the catalyst has higher activity and chemical stability, the apparent density is far greater than that of water (rho (ZrO) 2 )＝5.85g/cm 3 ，ρ(TiO 2 )＝4.23g/cm 3 ，ρ(CeO 2 )＝7.65g/cm 3 ) And is not suitable for being applied to an ozone catalytic fluidized bed reactor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ozone catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the invention provides an ozone catalyst, which comprises the following components in parts by weight: 10-20 parts of manganese ferrite, 40-65 parts of hollow fly ash floating beads, 10-15 parts of clay, 10-15 parts of glass powder and 2-7 parts of sodium alginate.
The manganese ferrite belongs to spinel ferrite, the ferrite can enrich hydroxyl groups on the surface of the catalyst, expose more lattice defects and active sites, and is beneficial to promoting the generation of more active species, and metal valence bonds formed between iron elements and divalent metal ions are stronger, so that the dissolution of the divalent metal elements can be effectively reduced, and the stability of the structure and the performance of the catalyst is maintained; in addition, the iron element has better magnetization performance, and is beneficial to recycling of materials. The invention uses the hollow fly ash as a framework component, effectively reduces the overall density of the catalyst, enables the apparent density to be close to water, and can realize the fluidization or floating state of the ozone catalytic reaction tank under the pushing of lower water power. The glass powder and the clay component are in a molten state at a high temperature, and the cooled catalyst has higher strength, is not easy to damage and has good stability. In the preparation and synthesis process of the catalyst, the weight ratio of different elements in the raw materials not only affects the surface chemical properties of the catalyst, but also can affect the physical structural characteristics of the catalyst, thereby affecting the activity of the catalyst. Sodium alginate is used as a carrier of a synthesis template, and the molding of catalyst embryo particles can be influenced by too much or too little concentration of sodium alginate in an aqueous solution.
As a preferred embodiment of the ozone catalyst of the present invention, the ozone catalyst comprises the following components in parts by weight: 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder and 5 parts of sodium alginate.
The catalytic effect and the density of the ozone catalyst are influenced by the component ratio of the ozone catalyst, and researches show that the catalytic effect and the density of the ozone catalyst are optimal when the components of the ozone catalyst are in the weight parts.
As a preferable embodiment of the ozone catalyst of the present invention, the particle size of the component is 100 to 400 mesh. The particle size of the catalyst component influences the catalytic effect and the particle strength of the catalyst.
In a second aspect, the present invention also provides a method for preparing an ozone catalyst, comprising the steps of:
(1) fully mixing manganese ferrite, hollow fly ash floating bead powder, clay and glass powder in water, adding sodium alginate, and placing in a water bath kettle for fully mixing to obtain a suspension;
(2) slowly adding the suspension obtained in the step (1) into a calcium chloride solution by using a peristaltic pump, and standing to obtain a catalyst precursor;
(3) and (3) drying the catalyst precursor obtained in the step (2), and then putting the dried catalyst precursor into a muffle furnace for roasting to obtain the ozone catalyst.
As a preferred embodiment of the preparation method of the ozone catalyst, the roasting is divided into two sections of roasting, wherein the first section is used for keeping the temperature for 1-2h at 600-700 ℃, and the second section is used for keeping the temperature for 1-2h when the temperature is raised to 900-1200 ℃.
The roasting temperature in the catalyst preparation process is a key technical parameter, and the catalytic performance of the prepared material under different temperature conditions has larger difference. When the roasting temperature is too high, the hydroxyl on the surface of the catalyst is condensed and dehydrated, so that the density of the hydroxyl on the surface of the catalyst is reduced, and the activity of the catalyst is reduced.
As a preferred embodiment of the preparation method of the ozone catalyst, the rotating speed of the peristaltic pump is 3-6rpm/min, and the mass fraction of calcium chloride in the calcium chloride solution is 1%.
As a preferred embodiment of the preparation method of the ozone catalyst, the peristaltic pump hose is one of the pipe numbers 82#, 86#, 88#, and 90 #.
In a third aspect, the invention also provides an application of the ozone catalyst in organic wastewater treatment.
As a preferred embodiment of the application of the ozone catalyst in the treatment of organic wastewater, the method comprises the following steps: (1) preparing organic wastewater with the pH value of 4-10 and the COD concentration of 70-170 mg/L; (2) then adding an ozone catalyst into the organic wastewater, and uniformly stirring; (3) then ozone is introduced for reaction for 30-60 min.
As a preferable embodiment of the application of the ozone catalyst in the organic wastewater treatment of the invention, the volume ratio of the ozone catalyst to the organic wastewater in the step (2) is (550-700) mL: 1L; the adding amount of the ozone in the step (3) is 20-70 mg/L sewage, and the aeration amount is 6.0-20.0L/h.
In water treatment processes, the efficiency of the degradation of contaminants is the ultimate goal. The important factor to be considered while maximizing the catalyst effect is the addition amount of the catalyst, and the optimal addition amount of the catalyst can maximize the economic efficiency and save the investment cost while ensuring the efficient removal of organic pollutants. The contact probability of ozone, pollutants and the catalyst in the system can be improved by increasing the adding amount of the catalyst, and meanwhile, the huge specific surface area of the catalyst also provides sufficient active point positions for the reaction, so that the efficient decomposition of the ozone is promoted to generate a larger amount of OH, and the degradation and removal of the pollutants are promoted; however, when the catalyst concentration is too high, the excess catalyst acts as a quencher for hydroxyl radicals, thereby reducing the removal effect of contaminants.
Ozone acts as a source of OH, the concentration of which directly affects the process treatment efficiency. Theoretically, the addition of ozone can improve the mass transfer efficiency of ozone in a liquid phase, promote the generation of OH and realize the high-efficiency removal of organic matters, but in the actual water treatment, the ozone is limited by the solubility of ozone and cannot be stably retained in an aqueous solution for a long time, so that the resource waste and the energy consumption cost are greatly increased, and the appropriate addition of ozone has great significance on the high efficiency and the economical efficiency of a heterogeneous catalysis ozone reaction system.
Ozone molecules are extremely unstable in water, and the pH value, temperature and the presence of organic matters of the solution can affect the ozone molecules in the solution to different degrees. Increase in solution pH, OH as chain reaction initiator - The relative concentration is increased continuously, and the self-decomposition of ozone to generate OH is accelerated. As the pH of the solution continues to increase, high concentrations of OH in the solution - The self-decomposition rate of ozone is greatly improved, and OH after the quantity reaches a threshold value is subjected to collision quenching immediately. Thus the pH>At 10, the radical utilization efficiency is greatly lowered.
Compared with the prior art, the invention has the beneficial effects that: the invention provides an ozone catalyst and a preparation method and application thereof, the ozone catalyst can obviously improve the catalytic efficiency, effectively remove organic pollutants in wastewater and simultaneously reduce the leaching of metal ions; the integral density of the ozone catalyst is close to that of water, and the fluidized bed state of the ozone catalytic reaction tank can be realized under the pushing of lower water power; the preparation method of the ozone catalyst is simple and easy to operate.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The embodiment provides an ozone catalyst, which comprises the following components: 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder, 5 parts of sodium alginate and 500 parts of water. The embodiment also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay and 15 parts of glass powder in 500 parts of water, then adding 5 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with the pipe diameter of 82#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1h at 700 ℃, heating to 1200 ℃, and preserving heat for 1h to obtain the ozone catalyst.
The embodiment also provides the application of the ozone catalyst in organic wastewater, which is realized by the following conditions:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Example 2
The embodiment provides an ozone catalyst, which comprises the following components: 15 parts of manganese ferrite, 65 parts of hollow fly ash floating beads, 12 parts of clay, 13 parts of glass powder, 2 parts of sodium alginate and 450 parts of water.
The embodiment also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 15 parts of manganese ferrite, 65 parts of hollow fly ash floating beads, 12 parts of clay and 13 parts of glass powder in 450 parts of water, then adding 2 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with a pipe diameter of 90#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 2h at 600 ℃, heating to 1100 ℃, and preserving heat for 1.5h to obtain the ozone catalyst.
The embodiment also provides the application of the ozone catalyst in organic wastewater, which is realized by the following conditions:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Example 3
The embodiment provides an ozone catalyst, which comprises the following components: 20 parts of manganese ferrite, 40 parts of hollow fly ash floating beads, 10 parts of clay, 10 parts of glass powder, 7 parts of sodium alginate and 550 parts of water.
The embodiment also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 20 parts of manganese ferrite, 40 parts of hollow fly ash floating beads, 10 parts of clay and 10 parts of glass powder in 550 parts of water, then adding 7 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at the rotating speed of 6rpm/min by using a peristaltic pump with the pipe diameter of 86# to form uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1.5h at 650 ℃, heating to 900 ℃, and preserving heat for 2h to obtain the ozone catalyst.
The embodiment also provides the application of the ozone catalyst in organic wastewater, which is realized by the following conditions:
(1) preparing bisphenol A simulated wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Example 4
The embodiment provides an ozone catalyst, which comprises the following components: 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder, 5 parts of sodium alginate and 500 parts of water. The embodiment also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay and 15 parts of glass powder in 500 parts of water, then adding 5 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with the pipe diameter of 82#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1h at 700 ℃, heating to 1200 ℃, and preserving heat for 1h to obtain the ozone catalyst.
The embodiment also provides the application of the ozone catalyst in organic wastewater, which is realized by the following conditions:
(1) preparing bisphenol A simulation wastewater with the pH value of 4 and the COD concentration of 70 mg/L; (2)550mL of the ozone catalyst is added into 1L of bisphenol A simulation wastewater, the mixture is uniformly stirred, and a 2L measuring cylinder is used as a reactor; (3) introducing bisphenol A simulated wastewater with the dosage of 20mg/L and ozone with the aeration rate of 15.0L/h for reaction for 45 min.
Example 5
The embodiment provides an ozone catalyst, which comprises the following components: 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder, 5 parts of sodium alginate and 500 parts of water. The embodiment also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay and 15 parts of glass powder in 500 parts of water, then adding 5 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with the pipe diameter of 82#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1h at 700 ℃, heating to 1200 ℃, and preserving heat for 1h to obtain the ozone catalyst.
The embodiment also provides the application of the ozone catalyst in organic wastewater, which is realized by the following conditions:
(1) preparing bisphenol A simulated wastewater with the pH value of 10 and the COD concentration of 170 mg/L; (2)700mL of the ozone catalyst is added into 1L of bisphenol A simulation wastewater, the mixture is uniformly stirred, and a 2L measuring cylinder is used as a reactor; (3) introducing 70mg/L bisphenol A simulated wastewater and 20.0L/h ozone for reaction for 60 min.
Comparative example 1
The present comparative example provides an ozone catalyst comprising the following components: 10 parts of ferric oxide, 55 parts of hollow fly ash floating bead, 15 parts of clay, 15 parts of glass powder, 5 parts of sodium alginate and 500 parts of water.
The comparative example also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 10 parts of ferric oxide, 55 parts of hollow fly ash floating beads, 15 parts of clay and 15 parts of glass powder in 500 parts of water, adding 5 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ for full dissolution to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with the pipe diameter of 82#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1h at 700 ℃, heating to 1200 ℃, and preserving heat for 1h to obtain the ozone catalyst.
The comparative example also provides the use of the above ozone catalyst in organic wastewater by:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Comparative example 2
The present comparative example provides an ozone catalyst comprising the following components: 10 parts of manganese dioxide, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder, 5 parts of sodium alginate and 500 parts of water.
The comparative example also provides a preparation method of the ozone catalyst, which comprises the following steps:
(1) uniformly dispersing the 10 parts of manganese dioxide, 55 parts of hollow fly ash floating beads, 15 parts of clay and 15 parts of glass powder in 500 parts of water, then adding 5 parts of sodium alginate, and placing the mixture in a water bath kettle at 60 ℃ to fully dissolve the mixture to obtain a suspension;
(2) adding the suspension into 500ml of 10g/L calcium chloride solution at a rotating speed of 3rpm/min by using a peristaltic pump with the pipe diameter of 82#, forming uniform gel balls, standing for 12h, and cleaning to obtain a catalyst precursor;
(3) and drying the precursor, placing the dried precursor in a muffle furnace, preserving heat for 1h at 700 ℃, heating to 1200 ℃, and preserving heat for 1h to obtain the ozone catalyst.
The comparative example also provides the use of the above ozone catalyst in organic wastewater by:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Comparative example 3
The ozone catalyst of this comparative example was non-catalytic glass particles as a separate ozone comparative example.
The comparative example also provides the use of the above ozone catalyst in organic wastewater by:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
Comparative example 4
The comparative example adopts a metal-doped ceramsite catalyst of the patent publication CN201911061136.2 as an ozone catalyst, and comprises the following steps:
(1) preparing bisphenol A simulation wastewater with the pH value of 6.7 and the COD concentration of 162 mg/L; (2) adding 600mL of the ozone catalyst into 1L of bisphenol A simulation wastewater, uniformly stirring, and using a 2L measuring cylinder as a reactor; (3) introducing 50mg/L bisphenol A simulated wastewater and 6.0L/h ozone for reaction for 30 min.
The concentrations of residual COD in the solutions of examples 1 to 5 and comparative examples 1 to 4 were determined by a Hausso COD Analyzer, and the concentrations of leached transition metals in the solutions of examples 1 to 5 and comparative examples 1 to 4 were determined by ICP. The COD removal rate and transition metal leach concentration data are shown in table 1.
TABLE 1
Figure BDA0002908593990000111
As can be seen from Table 1, in different fluidized bed ozone catalytic systems, compared to Fe alone 2 O 3 And MnO with MnO 2 Ozone catalyst as active component, Fe 2 O 3 The degradation rate of the catalyst to bisphenol A is 58 percent, and MnO is added 2 The degradation rate of the catalyst to the bisphenol A is 61 percent, and the degradation rate of the ozone catalyst to the bisphenol A is 73 percent, so that the degradation rate is obviously improved; on the other hand, the leaching of the metal ions after the reaction is not more than 1mg/L, which shows that the multi-metal catalyst has better catalytic effect.
Effect example 1
The ozone catalyst is compounded by adopting different components, so that the apparent density of the ozone catalyst is closer to the specific gravity of water while the catalytic effect is ensured, and the suspension state of the ozone catalyst in water is realized. In order to examine the influence of the component ratio, in the present effect example, the following test groups 1 to 12 of ozone catalysts were prepared according to the preparation method of the ozone catalyst in example 1, and the ozone catalyst in the present effect example was applied to organic wastewater according to the application of the ozone catalyst in example 1.
The concentration of the residual COD in the solution of the effect example was measured by a Harsu COD analyzer, and the concentration of the transition metal leached in the solution of the effect example was measured by ICP. The composition components, COD removal rate and transition metal leaching concentration data of the ozone catalysts of the test groups 1-12 are shown in Table 2.
TABLE 2
Figure BDA0002908593990000121
Comparing example 1 and effect example 1, it can be seen that only the ozone catalyst prepared within the range given by the present composition has both excellent catalytic effect and specific gravity closer to 1.0.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The ozone catalyst is characterized by comprising the following components in parts by weight: 10-20 parts of manganese ferrite, 40-65 parts of hollow fly ash floating beads, 10-15 parts of clay, 10-15 parts of glass powder and 2-7 parts of sodium alginate.
2. The ozone catalyst as claimed in claim 1, wherein the ozone catalyst comprises the following components in parts by weight: 10 parts of manganese ferrite, 55 parts of hollow fly ash floating beads, 15 parts of clay, 15 parts of glass powder and 5 parts of sodium alginate.
3. The ozone catalyst of claim 1, wherein the particle size of the component is 100 to 400 mesh.
4. The preparation method of the ozone catalyst is characterized by comprising the following steps of:
(1) fully mixing manganese ferrite, hollow fly ash floating bead powder, clay and glass powder in water, adding sodium alginate, and placing in a water bath kettle for fully mixing to obtain a suspension;
(2) slowly adding the suspension obtained in the step (1) into a calcium chloride solution by using a peristaltic pump, and standing to obtain a catalyst precursor;
(3) and (3) drying the catalyst precursor obtained in the step (2), and then putting the dried catalyst precursor into a muffle furnace for roasting to obtain the ozone catalyst.
5. The method for preparing the ozone catalyst according to claim 4, wherein the roasting is divided into two stages of roasting, the first stage is for heat preservation for 1-2h at 600-700 ℃, and the second stage is for heat preservation for 1-2h when the temperature is raised to 900-1200 ℃.
6. The method for preparing the ozone catalyst according to claim 4, wherein the rotation speed of the peristaltic pump is 3 to 6rpm/min, and the mass fraction of calcium chloride in the calcium chloride solution is 1%.
7. The method for preparing the ozone catalyst as claimed in claim 4, wherein the peristaltic pump hose is one of the hose numbers 82#, 86#, 88#, and 90 #.
8. Use of an ozone catalyst according to any one of claims 1 to 7 in the treatment of organic waste water.
9. Use of an ozone catalyst according to claim 8 in the treatment of organic waste water, comprising the steps of: (1) preparing organic wastewater with the pH value of 4-10 and the COD concentration of 70-170 mg/L; (2) then adding an ozone catalyst into the organic wastewater, and uniformly stirring; (3) then ozone is introduced for reaction for 30-60 min.
10. The use of the ozone catalyst in the treatment of organic wastewater according to claim 9, wherein the volume ratio of the ozone catalyst to the organic wastewater in the step (2) is (550-700) mL: 1L; the adding amount of the ozone in the step (3) is 20-70 mg/L of the organic wastewater, and the aeration amount is 6.0-20.0L/h.
CN202110079178.XA 2021-01-21 2021-01-21 Ozone catalyst and preparation method and application thereof Pending CN114797887A (en)

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Application publication date: 20220729