CN112138678A - Ozone catalytic oxidation catalyst and preparation method and application thereof - Google Patents
Ozone catalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN112138678A CN112138678A CN201910568525.8A CN201910568525A CN112138678A CN 112138678 A CN112138678 A CN 112138678A CN 201910568525 A CN201910568525 A CN 201910568525A CN 112138678 A CN112138678 A CN 112138678A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003245 coal Substances 0.000 claims abstract description 35
- 238000003763 carbonization Methods 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000004913 activation Effects 0.000 claims abstract description 18
- 239000012778 molding material Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 3
- 150000002909 rare earth metal compounds Chemical class 0.000 claims description 3
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 29
- 239000002351 wastewater Substances 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 238000001994 activation Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000011280 coal tar Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000005539 carbonized material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J23/76—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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides an ozone catalytic oxidation catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: mixing: providing coal powder, active components and an auxiliary agent, and mixing the coal powder, the active components and the auxiliary agent to form a mixture; a forming step: bonding the mixed materials together by a binder to form a molding material; a carbonization step: carbonizing the molding material; an activation step: and (3) activating the product obtained in the carbonization step to obtain the ozone catalytic oxidation catalyst. According to the preparation method disclosed by the invention, a double-pore distribution structure with mesopores and micropores in coexistence can be prepared, and the surface of the catalyst is chemically modified by additionally adding an auxiliary agent in the preparation process of the catalyst, so that the hydrophobicity of the activated carbon carrier catalyst is adjusted, and further the catalyst with different hydrophobicity is obtained, and therefore, the adsorption capacity of organic matters with different hydrophilicity and hydrophobicity in wastewater can be improved, and the removal capacity of the organic matters is further improved.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a preparation method of an ozone catalytic oxidation catalyst and the ozone catalytic oxidation catalyst obtained by the preparation method.
Background
With the development of industry, the demand for treating industrial wastewater difficult to degrade is increasingly urgent. The nondegradable substances in the industrial wastewater directly determine the standard discharge and stable operation of a sewage treatment plant. The traditional biochemical treatment method cannot remove toxic, harmful and other refractory substances in industrial wastewater, so that an advanced oxidation water treatment technology must be introduced.
In the advanced oxidation water treatment technology, the ozone catalytic oxidation method belongs to an important branch, and is used for oxidizing small molecular acid, macromolecules and organic matters which are difficult to biodegrade into low-toxicity or non-toxic small molecular substances. In the heterogeneous ozone catalytic oxidation reaction process, organic matters in the wastewater are firstly adsorbed on the surface of the catalyst and then are further degraded.
For the catalytic ozonation technology, the key technology is the preparation of the catalyst. However, the catalyst in the prior art has higher production cost and shorter service life due to the preparation process, thereby increasing the cost of sewage treatment.
Disclosure of Invention
The invention provides a preparation method of an ozone catalytic oxidation catalyst and the ozone catalytic oxidation catalyst obtained by the preparation method, and the preparation method not only can prepare a mesoporous and microporous dual-pore distribution structure, but also can modulate the hydrophobicity of an activated carbon carrier catalyst, thereby improving the adsorption capacity of organic matters with different hydrophilicity and hydrophobicity in wastewater and further improving the removal capacity of the organic matters.
According to an aspect of the present invention, there is provided a method for preparing an ozone catalytic oxidation catalyst, the method comprising: mixing: providing coal powder, active components and an auxiliary agent, and mixing the coal powder, the active components and the auxiliary agent to form a mixture; a forming step: bonding the mixed materials together by a binder to form a molding material; a carbonization step: carbonizing the molding material; an activation step: and activating the catalyst semi-finished product obtained in the carbonization step to obtain the ozone catalytic oxidation catalyst.
The active component may include at least one of a transition metal compound, a rare earth metal compound, an alkali metal compound, and an alkaline earth metal compound.
The mass of the active component can be 1-10% of the mass of the coal powder in percentage by weight.
The mass of the active component can be 1-5% of the mass of the coal powder in percentage by weight.
The auxiliary agent can comprise at least one of ammonium persulfate, citric acid and melamine.
The mass of the auxiliary agent can be 3-10% of the mass of the coal powder in percentage by weight.
In the carbonization step, the carbonization temperature can be 300-600 ℃, and the carbonization time can be 10-50 min.
In the activation step, water vapor can be used as an activating agent, the activation temperature can be 700-1000 ℃, the activation time can be 20-50 h, and the mass ratio of the introduced mass of the water vapor to the mass of the coal powder can be 10: 1-20: 1.
According to another aspect of the present invention, there is provided an ozone catalytic oxidation catalyst prepared by the above-mentioned preparation method.
According to another aspect of the invention, the application of the ozone catalytic oxidation catalyst prepared by the preparation method in sewage treatment is provided.
The inventive concept has been briefly described above. The invention discloses a method for carbonizing and activating a molding material comprising a coal powder carrier, an active component and an auxiliary agent by utilizing a carbonization and activation process, so that the adsorption capacity of the molding material on organic matters with different hydrophilicity and hydrophobicity in wastewater can be improved by modulating the hydrophobicity of an active carbon carrier catalyst, the removal capacity of the molding material is further improved, the COD removal rate is greatly improved, and the investment cost and the operation cost can be greatly reduced.
Detailed Description
Hereinafter, the inventive concept will be described in detail with reference to specific embodiments, however, the following specific embodiments are only intended to fully convey the inventive concept to those skilled in the art, and do not limit the scope of the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
For heterogeneous catalytic reactions, both adsorption and catalysis are important. The whole heterogeneous catalytic reaction process can be summarized into the following seven steps: diffusion of the reactant-diffusion of the reactant to the outer surface of the catalyst; indiffusion of reactants-diffusion of reactants at the outer surface of the catalyst into the pores of the catalyst; ③ chemical adsorption of reactants; fourthly, surface chemical reaction; desorbing the product; sixthly, the product is diffused in the reactor; and the product is diffused outwards. Chemical adsorption is an important step, and the chemical adsorption activates reactant molecules, so that the activation energy of chemical reaction is reduced. To facilitate the reaction, it is required that the chemisorption be neither too strong nor too weak. The adsorption particles are too strong to be transported, contacted and reacted on the surface; too weak will desorb and run off before the reaction.
The organic substances in the wastewater can be roughly divided into two categories of polar and nonpolar, and the majority of macromolecular organic substances are nonpolar and hydrophobic organic substances, and vice versa. The refractory organic matters in the industrial wastewater are mainly macromolecular organic matters.
In the existing ozone catalytic oxidation technology, the key of the ozone catalytic oxidation technology for treating organic matters in industrial wastewater is to decompose ozone into OH through the catalytic action of a catalyst. Because OH has a high potential (E)02.8V), strong reaction capability, fast reaction speed and can initiate chain reaction, thereby thoroughly degrading a plurality of organic matters. However, the survival time of OH is nanosecond and is generated on the surface of the catalyst, so that OH and organic substances cannot react at a position far from the surface of the catalyst. Therefore, the adsorption of the catalyst to organic matters is particularly important.
The chemical properties of the surface of the activated carbon carrier catalyst are different, so that the catalyst has certain selectivity on the adsorption of organic matters, and the migration and diffusion speed of the organic matters in the pores of the activated carbon carrier catalyst is influenced.
The inventive concept therefore seeks to modify the catalyst in the following ways: the hydrophobicity of the surface of the activated carbon carrier catalyst is modulated to modulate the adsorption of organic matters with different properties. However, it is not the case that the higher the hydrophobicity of the catalyst surface, the better, since too strong hydrophobicity affects the affinity of the activated carbon for water and thus the adsorption of organic substances in water by the activated carbon. Therefore, it is important to modulate the hydrophobicity of the activated carbon supported catalyst.
Therefore, the surface of the activated carbon carrier is modified by the aid of the auxiliary agent, and the hydrophobicity of the surface of the catalyst is modulated to improve the adsorption capacity of the catalyst on organic matters with different hydrophilicity and hydrophobicity, so that the removal capacity of the catalyst is further improved. The activated carbon carrier catalysts with different hydrophobicity can be obtained by adjusting the type and the dosage of the auxiliary agent, so that a series of activated carbon carrier catalysts with proper adsorbability to different water qualities can be further obtained.
Hereinafter, a method of preparing an ozone catalytic oxidation catalyst for treating wastewater according to an exemplary embodiment of the inventive concept will be described in detail.
A method of preparing an ozone catalytic oxidation catalyst for treating wastewater according to an exemplary embodiment of the present invention includes a mixing step, a molding step, a carbonization step, and an activation step. Hereinafter, the respective steps according to the inventive concept will be described in detail.
Mixing step
Providing coal powder, active components and auxiliary agents, and mixing the coal powder, the active components and the auxiliary agents to form a mixed material.
The coal powder is used as a carrier to load active components and auxiliary agents, and is used as a matrix for subsequent carbonization and activation reactions.
The active component is used to degrade organic matter and thus may be an active component known in the art for treating wastewater. For example, the active component according to an exemplary embodiment of the inventive concept may include at least one of a transition metal compound, a rare earth metal compound, an alkali metal compound, and an alkaline earth metal compound. Specifically, the active component according to an exemplary embodiment of the inventive concept may include at least one of potassium nitrate, iron nitrate, and manganese acetate. For example, in the case where the active components include potassium nitrate, iron nitrate, and manganese acetate, the molar ratio of the potassium nitrate, the iron nitrate, and the manganese acetate may be 1:4:2 to 1:8: 4. However, exemplary embodiments of the inventive concept are not limited to the above-described composition and specific formulation of the active components.
In addition, in order to enable the active component to be attached to the carrier in the largest amount and to efficiently degrade the organic matter, the added mass of the active component may be 1% to 10%, preferably 1% to 5% by weight of the mass of the pulverized coal.
The auxiliary agent is used for modulating the hydrophobicity of the activated carbon carrier catalyst, so that catalysts with different hydrophobicity can be obtained, and the adsorption of organic matters with different polarities in the refractory wastewater can be modulated. The auxiliary according to an exemplary embodiment may include, but is not limited to, one or more of ammonium persulfate, citric acid, and melamine. However, the inventive concept is not limited thereto. The active carbon is modified by the aid of the auxiliary agent, so that the hydrophobicity of the surface of the active carbon supported catalyst can be adjusted by the aid of the auxiliary agent. However, too strong hydrophobicity may affect the affinity of the catalyst for water. Therefore, the amount of the auxiliary needs to be controlled. According to exemplary embodiments of the inventive concept, the mass of the additive added may be 3% to 10% by weight of the mass of the pulverized coal.
Through the above description, by selectively using and mixing the pulverized coal, the active component and the auxiliary agent, a mixture material with the pulverized coal as a main matrix can be formed to provide a raw material for a subsequent molding step.
Shaping step
After the mixing step, a mixed (e.g., homogeneously mixed) mixture is obtained. The mixture is bonded together by the binder by adding the binder to the mixture to form the molding compound.
According to an exemplary embodiment, the binder may include coal tar. Here, since the coal tar has good wettability and binding power, it is possible to ensure that the paste (i.e., the mixture of the mix and the binder) has good plasticity. However, the inventive concept is not limited to coal tar as the binder. That is, the skilled person can use binders known in the art for shaping to achieve binding of the mix. For example, according to a specific example, a binder known in the art such as residual oil may be used instead of coal tar. For another example, two or more binders known in the art may be used to achieve the bonding of the mix.
After the binder is added to the mixture, the formed paste may be kneaded, and may be strip-formed in a forming apparatus such as a strip extruder, thereby obtaining a molding material.
Carbonization step
And carbonizing the molding material to obtain a carbonized material.
According to an exemplary embodiment of the inventive concept, the carbonization step may be performed in a carbonization furnace. According to an exemplary embodiment of the inventive concept, in the carbonizing step: the carbonization temperature can be controlled to be 300-600 ℃, and is preferably 400-500 ℃; the carbonization time can be controlled to be 10min-50min, preferably 20min-30 min.
Step of activation
In the activation furnace, water vapor can be used as an activating agent to activate the carbonized material for 20h-50h at the temperature of 700-1000 ℃, and the ratio of the mass of the introduced water vapor to the mass of the raw material coal can be 10: 1-20: 1, so that the finished product of the ozone catalytic oxidation catalyst is obtained.
After the above method, the catalytic ozonation catalyst for treating wastewater according to the present inventive concept can be prepared. According to the preparation method of the ozone catalytic oxidation catalyst, which is disclosed by the invention, a double-pore distribution structure with mesopores and micropores in coexistence can be prepared, and the surface of the catalyst is chemically modified by adding an auxiliary agent in the preparation process of the catalyst, so that the hydrophobicity of the activated carbon carrier catalyst is adjusted, and further the catalyst with different hydrophobicity is obtained, the adsorption of organic matters with different polarities in the refractory wastewater is adjusted, and then the refractory wastewater is further subjected to oxidative degradation.
The method of preparing the catalytic oxidation catalyst for ozone for treating wastewater according to the exemplary embodiments of the inventive concept is described above in detail with reference to the exemplary embodiments. Wherein a description of some well-known techniques is omitted so as to more fully convey the concept of the present invention to those skilled in the art.
Hereinafter, specific embodiments of the inventive concept and comparative examples will be described.
Example 1
The preparation method of the ozone catalytic oxidation catalyst of example 1 includes the steps of:
A) crushing 100g of raw material coal by using a crusher until the granularity is not more than 75 mu m, then adding 1g of active component and 3g of ammonium persulfate, uniformly mixing, then adding 5g of coal tar for kneading, and extruding and molding in a strip extruder to obtain a molding material;
B) placing the molding material in a carbonization furnace, carbonizing at 300 ℃ for 10min under an anaerobic condition, and discharging and cooling from an outlet after carbonization is finished; and then putting the carbonized material after carbonization into an activation furnace, activating for 20h at 700 ℃ by taking water vapor as an activating agent, wherein the mass ratio of the introduced amount of the water vapor to the raw material coal is 10:1, and finally obtaining the ozone catalytic oxidation catalyst A.
Wherein the active component is KNO3、Fe(NO3)3And manganese acetate (MnAC)2) The molar ratios of the three compounds were about 1:4:2, with masses of 0.04g, 0.71g and 0.25g, respectively. When in use, the three substances are respectively prepared into 10 percent aqueous solution by mass, namely 0.04g of KNO3Dissolving in 0.36g of water to obtain 0.71g of Fe (NO)3)3Dissolved in 6.39g of water, 0.25g of MnAC2Dissolved in 2.25g of water. Then adding the prepared water solution of the active component into the pulverized raw material coal powder and uniformly mixing.
Example 2
The preparation method of the ozone catalytic oxidation catalyst of example 2 includes the steps of:
A) crushing 100g of raw material coal by using a crusher to the particle size of not more than 75 mu m, adding 10g of active component and 10g of citric acid, uniformly mixing, adding 20g of coal tar, kneading, extruding in a strip extruder, and forming to obtain a forming material;
B) placing the molding material in a carbonization furnace, carbonizing at 600 ℃ for 50min under an anaerobic condition, and discharging and cooling from an outlet after carbonization is finished; and then putting the carbonized material after carbonization into an activation furnace, activating for 50h at 1000 ℃ by taking water vapor as an activating agent, wherein the mass ratio of the introduced amount of the water vapor to the raw material coal is 20:1, and finally obtaining the ozone catalytic oxidation catalyst B.
Wherein the active component is KNO3、Fe(NO3)3And MnAC2The molar ratios were about 1:4:2 for the three compounds at 0.41g, 7.07g and 2.52g, respectively. When in use, the three substances are respectively prepared into 10 percent aqueous solution by mass, namely 0.41g of KNO3Dissolved in 3.69g of water, 7.07g of Fe (NO)3)3Dissolved in 63.63g of water, 2.52g of MnAC2Dissolved in 22.68g of water. Then adding the prepared water solution of the active component into the pulverized raw material coal powder and uniformly mixing.
Example 3
The preparation method of the ozone catalytic oxidation catalyst of example 3 includes the steps of:
A) crushing 100g of raw material coal by using a crusher until the granularity is not more than 75 mu m, then adding 5g of active component and 5g of melamine, uniformly mixing, then adding 5g of coal tar for kneading, and extruding and molding in a strip extruder to obtain a molding material;
B) placing the molding material in a carbonization furnace, carbonizing at 400 ℃ for 30min under an anaerobic condition, and discharging and cooling from an outlet after carbonization is finished; and then placing the carbonized material after carbonization in an activation furnace, activating for 30h at 800 ℃ by using water vapor as an activating agent, wherein the mass ratio of the introduced amount of the water vapor to the raw material coal is 10:1, and finally obtaining the ozone catalytic oxidation catalyst C.
Wherein the active component is KNO3、Fe(NO3)3And MnAC2The molar ratios of the three compounds were about 1:4:2, with masses of 0.21g, 3.53g and 1.26g, respectively. When in use, the medicine is prepared fromThe three substances are respectively prepared into 10 percent aqueous solution by mass fraction, namely 0.21g of KNO3Dissolved in 1.89g of water, 3.53g of Fe (NO)3)3Dissolved in 31.77g of water, 1.26g of MnAC2Dissolved in 11.34g of water. Then adding the prepared water solution of the active component into the crushed raw material coal and mixing uniformly.
Comparative example
The preparation method of the ozone catalytic oxidation catalyst of the comparative example comprises the following steps:
A) crushing 100g of raw material coal by using a crusher to the granularity of not more than 75 mu m, adding 10g of active component, uniformly mixing, adding 5g of coal tar, kneading, extruding in a strip extruder, and forming to obtain the forming material.
B) Placing the molding material in a carbonization furnace, carbonizing at 400 ℃ for 50min under an anaerobic condition, and discharging and cooling from an outlet after carbonization is finished; and then placing the carbonized material after carbonization in an activation furnace, activating for 30h at 800 ℃ by using water vapor as an activating agent, wherein the mass ratio of the introduced amount of the water vapor to the raw material coal is 15: 1, and finally obtaining the ozone catalytic oxidation catalyst D.
Wherein the active component is KNO3、Fe(NO3)3And MnAC2The molar ratios were about 1:4:2 for the three compounds at 0.41g, 7.07g and 2.52g, respectively. When in use, the three substances are respectively prepared into 10 percent aqueous solution by mass, namely 0.41g of KNO3Dissolved in 3.69g of water, 7.07g of Fe (NO)3)3Dissolved in 63.63g of water, 2.52g of MnAC2Dissolved in 22.68g of water. Then adding the prepared water solution of the active component into the crushed raw material coal and mixing uniformly.
The catalysts a to D prepared in examples 1 to 3 and comparative example were subjected to evaluation of the ozone catalytic oxidation test of wastewater under the following evaluation conditions and test results: the catalysts A-D are all used in a fixed bed reactor for treating wastewater, and the wastewater comprises medicine, pesticide, pigment, fertilizer and spice wastewater, wherein the pigment wastewater is mainly used, the COD content is about 100mg/L, and the chloride ion content is lower than 2000 mg/L.
The volume of the catalyst bed layer is 2L, and the space velocity of the wastewater volume is 1h-1The ozone concentration is 100mg/L, and the ozone adding amount is 70 mg/L. The COD removal rates of the wastewater in the continuous runs at room temperature for 3h, 4h and 5h are shown in Table 1.
TABLE 1 evaluation test results of catalyst treatment wastewater performance
As can be seen from table 1, the COD removal rate of the ozone catalytic oxidation catalyst prepared using the preparation method according to the inventive concept was significantly higher than that of the catalyst of the comparative example.
Example embodiments have been disclosed herein and, although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone, or in combination with features, characteristics and/or elements described in connection with other embodiments, as would be apparent to one of ordinary skill in the art upon submission of the present application, unless explicitly stated otherwise. It will therefore be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as set forth in the appended claims.
Claims (10)
1. A preparation method of an ozone catalytic oxidation catalyst is characterized by comprising the following steps:
mixing: providing coal powder, active components and an auxiliary agent, and mixing the coal powder, the active components and the auxiliary agent to form a mixture;
a forming step: bonding the mixed materials together by a binder to form a molding material;
a carbonization step: carbonizing the molding material;
an activation step: and activating the product obtained in the carbonization step to obtain the ozone catalytic oxidation catalyst.
2. The production method according to claim 1, wherein the active component includes at least one of a transition metal compound, a rare earth metal compound, an alkali metal compound, and an alkaline earth metal compound.
3. The preparation method according to claim 2, wherein the mass of the active component is 1-10% of the mass of the pulverized coal in percentage by weight.
4. The preparation method according to claim 3, wherein the mass of the active component may be 1 to 5% by weight of the mass of the pulverized coal.
5. The preparation method according to claim 1, wherein the auxiliary agent comprises at least one of ammonium persulfate, citric acid and melamine.
6. The preparation method according to claim 5, wherein the mass of the auxiliary agent is 3-10% of the mass of the pulverized coal in percentage by weight.
7. The preparation method according to claim 1, wherein in the carbonization step, the carbonization temperature is 300 ℃ to 600 ℃ and the carbonization time is 10min to 50 min.
8. The preparation method according to claim 1, wherein in the activation step, steam is used as an activating agent, the activation temperature is 700-1000 ℃, the activation time is 20-50 h, and the ratio of the mass of introduced steam to the mass of the pulverized coal is 10: 1-20: 1.
9. An ozone catalytic oxidation catalyst prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the ozone catalytic oxidation catalyst prepared by the preparation method according to any one of claims 1 to 8 in sewage treatment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680349A (en) * | 2021-09-28 | 2021-11-23 | 中冶南方都市环保工程技术股份有限公司 | Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater |
| CN114289027A (en) * | 2021-11-24 | 2022-04-08 | 山东华特环保科技有限公司 | Efficient composite ozone catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150375197A1 (en) * | 2013-02-20 | 2015-12-31 | Osaka Gas Chemicals Co., Ltd. | Granular activated carbon having many mesopores, and manufacturing method for same |
| CN108057455A (en) * | 2017-12-28 | 2018-05-22 | 天津碧水源膜材料有限公司 | Ozone catalytic oxidation catalyst and its preparation method and application |
| WO2018099173A1 (en) * | 2016-12-02 | 2018-06-07 | 建添企业有限公司 | Method for preparing nitrogen-doped porous carbon material by using coal as raw material |
| CN207646030U (en) * | 2018-01-08 | 2018-07-24 | 金风环保有限公司 | A kind of novel ozone activated carbon combination unit |
| CN108404950A (en) * | 2017-02-09 | 2018-08-17 | 邢台旭阳科技有限公司 | A method of handling industrial wastewater for the catalyst of catalytic ozonation, preparation method and using it |
-
2019
- 2019-06-27 CN CN201910568525.8A patent/CN112138678A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150375197A1 (en) * | 2013-02-20 | 2015-12-31 | Osaka Gas Chemicals Co., Ltd. | Granular activated carbon having many mesopores, and manufacturing method for same |
| WO2018099173A1 (en) * | 2016-12-02 | 2018-06-07 | 建添企业有限公司 | Method for preparing nitrogen-doped porous carbon material by using coal as raw material |
| CN108404950A (en) * | 2017-02-09 | 2018-08-17 | 邢台旭阳科技有限公司 | A method of handling industrial wastewater for the catalyst of catalytic ozonation, preparation method and using it |
| CN108057455A (en) * | 2017-12-28 | 2018-05-22 | 天津碧水源膜材料有限公司 | Ozone catalytic oxidation catalyst and its preparation method and application |
| CN207646030U (en) * | 2018-01-08 | 2018-07-24 | 金风环保有限公司 | A kind of novel ozone activated carbon combination unit |
Non-Patent Citations (1)
| Title |
|---|
| 熊道陵等: "《碳纳米管的结构性能、合成及其应用》", 黑龙江大学出版社, pages: 230 - 231 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680349A (en) * | 2021-09-28 | 2021-11-23 | 中冶南方都市环保工程技术股份有限公司 | Preparation method of coal-based active coke-based ozone catalyst for treating coking wastewater |
| CN114289027A (en) * | 2021-11-24 | 2022-04-08 | 山东华特环保科技有限公司 | Efficient composite ozone catalyst and preparation method and application thereof |
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