CN115193445B - Preparation method of three-dimensional electrocatalytic oxidation catalyst by mechanochemical method - Google Patents
Preparation method of three-dimensional electrocatalytic oxidation catalyst by mechanochemical method Download PDFInfo
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- CN115193445B CN115193445B CN202110379281.6A CN202110379281A CN115193445B CN 115193445 B CN115193445 B CN 115193445B CN 202110379281 A CN202110379281 A CN 202110379281A CN 115193445 B CN115193445 B CN 115193445B
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- 238000003763 carbonization Methods 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000005751 Copper oxide Substances 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003830 anthracite Substances 0.000 claims description 7
- 239000011280 coal tar Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
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- 238000000498 ball milling Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
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- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 150000004706 metal oxides Chemical class 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 11
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- 238000005303 weighing Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
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- 238000004898 kneading Methods 0.000 description 2
- -1 metal oxide nitride Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 239000010411 electrocatalyst Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
-
- B01J35/33—
-
- 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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/72—Copper
-
- 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
-
- B01J35/617—
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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]
Abstract
The invention provides a method for preparing a three-dimensional electrocatalytic oxidation catalyst by using a mechanochemical method, the catalyst comprises a carrier and a catalyst active component loaded on the carrier, wherein the catalyst active component is one or more selected from metal oxides and metal hydroxides, the catalyst carrier is powder, the active component is loaded on the catalyst carrier by adopting a grinding method, the preparation method ensures that the catalyst active component on the catalyst carrier is more uniformly distributed, the number of catalytic active sites is effectively increased, the catalytic activity of the prepared catalyst is greatly improved, and the preparation method is simple and does not generate SO in the preparation process 2 、NO 2 The emission has the advantage of environmental friendliness.
Description
Technical Field
The invention belongs to the field of environmental purification, and particularly relates to a high-efficiency preparation method of a three-dimensional electrocatalytic oxidation catalyst by a mechanochemical method.
Background
At present, the two demands show explosive growth regarding advanced oxidation pretreatment of refractory industrial wastewater to improve the biodegradability of the wastewater and advanced oxidation advanced treatment of biochemical effluent to further improve the wastewater treatment effect. Wherein Fenton reaction, ozone catalytic oxidation, electrocatalytic oxidation and the like are several advanced oxidation techniques commonly used in the industry. The three-dimensional electrocatalytic oxidation can generate more original ecological H in the same time and space under the action of the three-dimensional electrocatalytic principle because the electrocatalytic oxidation reaction vessel is internally filled with the electrocatalytic catalyst to form a three-dimensional battery 2 O 2 And hydroxyl free radicals, thereby achieving better electrocatalytic oxidation effect, excellent performance and increasing application.
In the current literature report, the preparation process of the disclosed three-dimensional electrocatalytic oxidation catalyst adopts the principle of an impregnation method, and has the common characteristics that: and (3) dipping and adsorbing transition metal nitrate on the formed catalyst carrier, and then drying and roasting to obtain a final catalyst product. The preparation method has long process flow, and the product prepared by the impregnation method has natural defect of uneven distribution of active components, so that the catalytic effect of the active components can not be fully exerted in practical application, and in addition, the transition metal nitrate is used as an active component precursor, NO can be released in the roasting process 2 There are problems of resource waste and environmental pollution.
Therefore, the invention provides a high-efficiency preparation method of the three-dimensional electrocatalytic oxidation catalyst with simple flow.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the catalyst disclosed by the invention is prepared by adopting metal oxide or hydroxide as the active component of the catalyst, grinding the active component and a catalyst carrier, forming the active component, and carbonizing the active component and the catalyst carrier.
In a first aspect, the present invention provides a three-dimensional electrocatalytic oxidation catalyst comprising a support and a catalyst active component supported on the support by mechanical attrition,
the catalyst active component is selected from one or more of metal oxide and metal hydroxide, and the catalyst carrier is in a powder form.
A second aspect of the present invention is to provide a method for preparing the three-dimensional electrocatalytic oxidation catalyst according to the first aspect of the present invention, comprising the steps of:
step 1, mixing a catalyst active component and a catalyst carrier;
step 2, grinding the mixture obtained in the step 1 and then forming;
and 3, carbonizing the molded substance obtained in the step 2.
A third aspect of the present invention is to provide the use of a three-dimensional electrocatalytic oxidation catalyst according to the first aspect of the present invention or prepared by a method of preparation according to the second aspect of the present invention, for treating sewage.
The preparation method of the three-dimensional electrocatalytic oxidation catalyst by using the mechanochemical method provided by the invention has the following advantages:
(1) The preparation method of the three-dimensional electrocatalytic oxidation catalyst has simple flow and higher preparation efficiency;
(2) The surfaces of the active component catalyst particles in the catalyst prepared by the preparation method of the three-dimensional electrocatalytic oxidation catalyst are uniformly distributed, so that the number of catalytic active sites is effectively increased, and the catalytic activity is greatly improved;
(3) The preparation method of the three-dimensional electrocatalytic oxidation catalyst does not generate SO in the preparation process 2 、NO 2 The emission has the advantage of environmental friendliness;
(4) The three-dimensional electrocatalytic oxidation catalyst has the advantages of larger specific surface area, higher mechanical strength and good COD removal efficiency.
Drawings
FIG. 1 shows a scanning electron micrograph of a three-dimensional electrocatalytic oxidation catalyst prepared in example 1 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
A first aspect of the present invention is to provide a three-dimensional electrocatalytic oxidation catalyst comprising a support and a catalyst active component supported on the support by mechanical attrition.
The catalyst active component is selected from one or more of metal oxide and metal hydroxide, and the catalyst carrier is in a powder form.
According to the present invention, the catalyst active component is preferably one or more of metal oxides, more preferably one or more selected from oxides of manganese and copper, such as manganese dioxide (MnO) 2 ) And copper oxide (CuO).
In the present invention, the catalyst active component is selected from one or more of metal oxide and metal hydroxide, SO that SO generated during the preparation process due to the use of other metal compounds such as metal sulfate or nitrate can be avoided 2 、NO 2 And the like, so that the preparation process is safer and more environment-friendly.
The content of the catalyst active component in the catalyst is 0.5 to 20%, preferably the content of the catalyst active component in the catalyst is 1 to 15%, more preferably the content of the catalyst active component in the catalyst is 2 to 10%.
According to a preferred embodiment of the invention, the content of manganese dioxide in the catalyst is 2% -12%, and the content of copper oxide in the catalyst is 0.5% -5%; preferably, the content of manganese dioxide in the catalyst is 5% -10%, and the content of copper oxide in the catalyst is 1% -3%; more preferably, the manganese dioxide content in the catalyst is 6% and the copper oxide content in the catalyst is 1%.
Experiments show that the content of the active component of the catalyst can influence the mechanical strength of the finally prepared catalyst and the removal rate of COD in sewage, if the content of the active component is high, the removal rate of COD in sewage is high, but the improvement of the mechanical strength is not facilitated, and if the content of the active component is low, the removal rate of COD in sewage is reduced, but the mechanical strength is improved. When the content of the active component in the catalyst is 0.5-20%, the prepared catalyst has high mechanical strength and COD removal rate.
In the present invention, the catalyst support is in the form of powder, preferably one or more selected from diatomaceous earth, alumina and anthracite dust, more preferably from diatomaceous earth, alumina or anthracite dust.
The specific surface area of the three-dimensional electrocatalytic oxidation catalyst is 550-700 m 2 The mechanical strength of the catalyst is 90-98N/cm, and the removal rate of COD in sewage is 45-70%.
In the present invention, the three-dimensional electrocatalytic oxidation catalyst as described in the present invention is prepared by a process comprising the steps of:
step 1, mixing a catalyst active component and a catalyst carrier;
step 2, grinding the mixture obtained in the step 1 and then forming;
and 3, carbonizing the molded substance obtained in the step 2.
A second aspect of the present invention provides a method for preparing the three-dimensional electrocatalytic oxidation catalyst according to the first aspect of the present invention, the method comprising the steps of:
step 1, mixing a catalyst active component and a catalyst carrier;
step 2, grinding the mixture obtained in the step 1 and then forming;
and 3, carbonizing the molded substance obtained in the step 2.
This step is specifically described and illustrated below.
Step 1, mixing the catalyst active component with a catalyst carrier.
In the present invention, the catalyst active component is selected from one or more of metal oxides and metal hydroxides, preferablySelected from one or more of metal oxides, more preferably one or more of oxides of manganese and copper, such as manganese dioxide (MnO) 2 ) And copper oxide (CuO).
The inventor discovers that when the catalyst active component is selected from one or more of oxides of manganese and copper, the prepared three-dimensional electrocatalytic oxidation catalyst has larger specific surface area and higher mechanical strength, and has higher removal efficiency of COD in sewage. Particularly, when the active components of the catalyst are a mixture of manganese dioxide and copper oxide, the activation energy of the catalytic oxidation reaction of organic molecules can be reduced through the synergistic catalysis between the two metal oxides, the degradation of reaction intermediates can be accelerated, and the reaction rate and the catalytic activity can be improved, so that the removal efficiency of the prepared catalyst on COD in sewage is high.
The catalyst carrier is in a powder form, preferably one or more selected from diatomite, alumina and anthracite powder, more preferably selected from diatomite, alumina or anthracite powder.
The selection of the catalyst carrier can influence the specific surface area and COD removal rate of the prepared catalyst, and experiments show that the three-dimensional electrocatalytic oxidation catalyst prepared by taking anthracite powder as the catalyst carrier has larger specific surface area and good COD removal rate.
According to the invention, the mass ratio of the catalyst active component to the catalyst carrier is 1: (10 to 20), preferably 1: (10 to 15), more preferably 1: (12-14).
According to a preferred embodiment of the invention, when the catalyst active component selected is a mixture of manganese dioxide and copper oxide, the mass ratio of manganese dioxide to catalyst support is 1: (5-20), the mass ratio of the copper oxide to the catalyst carrier is 1: (70-110); preferably, the mass ratio of manganese dioxide to the catalyst carrier is 1, (10-17), and the mass ratio of copper oxide to the catalyst carrier is 1: (80-100); more preferably, the mass ratio of manganese dioxide to catalyst support is 1:15 and the mass ratio of copper oxide to catalyst support is 1:90.
Experiments show that the ratio of the catalyst active component to the catalyst carrier can influence the performance of the finally prepared catalyst, particularly has larger influence on the mechanical strength and the removal rate of COD in sewage, if the catalyst active component is used in a large amount, the prepared catalyst has high content of the active component and high removal rate of COD in sewage, but the mechanical strength is reduced, if the catalyst active component is used in a small amount, the removal rate of COD in sewage is reduced, the mechanical strength is improved, and when the mass ratio of the catalyst active component to the catalyst carrier is 1: and (10-20), the prepared catalyst has high mechanical strength and COD removal rate.
And 2, grinding the mixture obtained in the step 1 and then forming.
The mixture obtained in step 1 is milled, preferably in a ball mill, more preferably with a particle size of the milled mixture of less than 50 μm.
The preparation method overcomes the defects of long process flow, poor preparation environmental conditions, uneven distribution of active components in the prepared catalyst, incapability of fully playing the catalytic effect of the active components and the like in the preparation method of the catalyst by the impregnation method, greatly shortens the preparation flow of the catalyst by a mechanical grinding mode, and ensures that the active components in the prepared catalyst are uniformly distributed.
The milled mass is shaped, preferably with the addition of a binder, more preferably in a kneader.
The binder is a guarantee of the bonding strength between the abrasive and the matrix, and the addition of the binder can improve the strength of the product and prevent powder segregation, and can be removed before or during sintering.
The binder is selected from one or more of coal tar, soluble starch, polyvinyl alcohol, polyacrylate and carboxymethyl cellulose, preferably from one or more of coal tar, soluble starch and polyvinyl alcohol, more preferably from coal tar, soluble starch or polyvinyl alcohol.
When the soluble starch and the polyvinyl alcohol are used as the binder, the soluble starch and the polyvinyl alcohol are dissolved in water and then mixed with materials for forming, coal tar is used as the binder for direct addition forming, and meanwhile, the catalyst prepared by using the coal tar as the binder is found to have higher removal rate of COD in sewage.
The mass ratio of the binder to the catalyst carrier is 1: (5-15), preferably 1: (5-12), more preferably 1:9.
The kneaded material to which the binder is added is molded, preferably by extrusion molding, more preferably by extrusion molding in a column molding machine. The shaped product is preferably columnar.
In the invention, the catalyst is made into a column shape, so that the catalyst is more convenient to fill in the reactor when in use, and is more convenient to separate from wastewater after use.
And 3, carbonizing the molded substance obtained in the step 2.
Carbonizing the product formed in step 2, preferably in a carbonizing roasting furnace.
The carbonization is performed in a shielding gas, preferably argon or nitrogen shielding gas, more preferably nitrogen shielding gas.
According to the invention, the carbonization is a low temperature carbonization, the carbonization temperature being 200-600 ℃, preferably 300-500 ℃, more preferably 400-500 ℃, for example 450 ℃.
The carbonization time is 10 to 120min, preferably 15 to 90min, more preferably 30 to 60min, for example 45min.
The carbonization temperature and the carbonization time can influence the performance of the finally prepared catalyst, and experiments show that the low-temperature carbonization is more beneficial to the improvement of the catalyst performance, and particularly the catalyst obtained by carbonization has larger specific surface area, higher mechanical property and good COD removal rate when the carbonization temperature is 200-600 ℃ and the carbonization time is 10-120 min.
A third aspect of the present invention is to provide a three-dimensional electrocatalytic oxidation catalyst according to the first aspect of the present invention or a three-dimensional electrocatalytic oxidation catalyst prepared by the preparation method according to the second aspect of the present invention for use in the field of wastewater treatment, which has a high removal rate of COD in wastewater of 45% to 70%.
The invention has the beneficial effects that:
(1) The preparation method of the three-dimensional electrocatalytic oxidation catalyst has simple flow, and avoids the defects of complex preparation process methods of conventional catalysts such as impregnation, coprecipitation and the like;
(2) The preparation method of the three-dimensional electrocatalytic oxidation catalyst adopts a mechanochemical grinding method, so that the active components of the catalyst can be uniformly mixed with the carrier, and the catalyst can be uniformly distributed on the surface of the catalyst particles after being molded, thereby effectively increasing the number of catalytic active sites and greatly improving the catalytic activity;
(3) The preparation method of the three-dimensional electrocatalytic oxidation catalyst adopts oxides of manganese, copper and iron as active components, and does not generate SO in the preparation process 2 、NO 2 The emission has the advantage of environmental friendliness;
(4) The three-dimensional electrocatalytic oxidation catalyst has larger specific surface area, and the specific surface area can reach 660m at most 2 And/g, has higher mechanical strength, the mechanical strength is 90-98N/cm, and the highest COD removal efficiency can reach 65%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
Weighing 90g of anthracite and 6g of MnO 2 1g of CuO, putting the three materials into a ball mill together for ball milling until the granularity is less than 50 mu m, transferring the materials into a kneader, adding 10g of coal tar for kneading, and extruding by a columnar forming machine to obtain columnar formed products; transferring the molded product into a carbonization roasting furnace, carbonizing for 45min at 450 ℃ under the protection of nitrogen to obtain a final catalyst product, weighing 100g of catalyst, wherein the weight of the catalyst is MnO 2 6% of CuO and 1%.
Example 2
90g of diatomite and 6g of MnO are weighed 2 1g of CuO, putting the three materials into a ball mill together until the granularity is less than 50 mu m, transferring the materials into a kneader, adding water containing 10g of soluble starchKneading the solution, and extruding the solution by a columnar forming machine to obtain columnar formed products; transferring the molded product into a carbonization roasting furnace, carbonizing for 45min at 450 ℃ under nitrogen atmosphere to obtain a final catalyst product, weighing 100g of catalyst, and obtaining MnO (metal oxide nitride) 2 6% of CuO and 1%.
Example 3
Weighing 90g of alumina and 6g of MnO 2 1g of CuO, putting the three materials into a ball mill together for ball milling until the granularity is lower than 50 mu m, transferring the materials into a kneader, adding an aqueous solution containing 10g of polyvinyl alcohol for kneading, and extruding by a columnar forming machine to obtain columnar formed products; transferring the molded product into a carbonization roasting furnace, carbonizing for 45min at 450 ℃ under nitrogen atmosphere to obtain a final catalyst product, weighing 100g of catalyst, and obtaining MnO (metal oxide nitride) 2 6% of CuO and 1%.
Example 4
A catalyst product was prepared in a similar manner to example 1 except that MnO was not added 2 。
Example 5
A catalyst product was prepared in a similar manner to example 1 except that CuO was not added.
Experimental example
Experimental example 1 specific surface area test
Specific surface area tests were conducted on the catalyst samples prepared in examples 1 to 5, and the test results are shown in table 1.
As can be seen from Table 1, the catalyst prepared by the invention has a large specific surface area, and the specific surface area is 550-700 m 2 /g。
Experimental example 2 mechanical Strength test
The catalyst samples prepared in examples 1 to 5 were subjected to mechanical strength test, and the test results are shown in Table 1.
As can be seen from Table 1, the catalyst prepared by the invention has the mechanical strength of 90-98N/cm and higher mechanical strength, and meets the use standard of the electrocatalytic oxidation catalyst.
Experimental example 3 COD removal test
COD removal rate test was performed on the catalyst samples prepared in examples 1 to 5, and the electrocatalytic oxidation reaction effect was examined. The experimental parameters are as follows: graphite is adopted for both the cathode and the anode, the voltage is 10V, the distance between the electrodes is 10cm, the catalysts prepared in the examples 1-3 are respectively filled between the cathode and the anode, and the oxidation reaction time of the electrocatalyst is 30min. The experimental water sample adopts the biochemical effluent of the industrial wastewater which is difficult to degrade. The test results are shown in Table 1. Wherein the COD concentration of the inlet water before treatment is 190mg/L, and the COD removal rate= (concentration before treatment-concentration after treatment)/concentration before treatment is multiplied by 100%.
Table 1 examples 1 to 5 catalyst performance test results were obtained
As can be seen from Table 1, the catalyst samples prepared by the method have higher COD removal rate, the COD removal rate is 45% -70%, the catalyst prepared by the example 1 has the largest specific surface area, the COD removal efficiency is also the highest, and the catalyst prepared by the example 2 has the highest mechanical strength.
As can be seen from comparative examples 1 and 4 and examples 1 and 5, the COD removal rates of examples 4 and 5 were lower than those of the catalyst prepared in example 1, indicating that the catalyst has higher catalytic activity than the catalyst having only copper oxide or manganese dioxide as the active component when the active component of the catalyst is a mixture of copper oxide and manganese dioxide.
The catalyst prepared by the method can greatly catalyze and degrade COD, has industrial use conditions, and has high industrial scale-up feasibility.
Experimental example 4 SEM test
The catalyst sample prepared in example 1 of the present invention was subjected to scanning electron microscopy, and the test results are shown in fig. 1.
As can be seen from fig. 1, the catalyst exhibits a porous structure, and the active components are more uniformly distributed in the carrier.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (3)
1. The use of a three-dimensional electrocatalytic oxidation catalyst for wastewater treatment, characterized in that the three-dimensional electrocatalytic oxidation catalyst comprises a carrier and a catalyst active component supported on the carrier by mechanical grinding,
the active component of the catalyst is manganese dioxide MnO 2 And copper oxide CuO;
the catalyst carrier is one or more selected from diatomite, alumina and anthracite powder,
the method comprises the following steps:
step 1, mixing a catalyst active component and a catalyst carrier;
step 2, ball milling and molding the mixture obtained in the step 1;
step 3, carbonizing the molded substance obtained in the step 2,
in the step (1) of the process,
the mass ratio of the catalyst active component to the catalyst carrier is 1: (10-15), the mass ratio of manganese dioxide to the catalyst carrier is 1, (10-17), and the mass ratio of copper oxide to the catalyst carrier is 1: (80-100);
in the step 2, a binder is added for molding, wherein the binder is one or more selected from coal tar, soluble starch, polyvinyl alcohol, polyacrylate and carboxymethyl cellulose;
the mass ratio of the binder to the catalyst carrier is 1: (5-15);
in the step 3 of the method, in the step (3),
the carbonization is carried out in protective gas, the carbonization temperature is 200-600 ℃, and the carbonization time is 10-120 min.
2. Use according to claim 1, characterized in that the mass ratio of binder to catalyst support is 1: (5-12).
3. The use according to claim 1, characterized in that,
the specific surface area of the three-dimensional electrocatalytic oxidation catalyst is 550-700 m 2 The mechanical strength of the catalyst is 90-98N/cm, and the removal rate of COD in sewage is 45-70%.
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