CN113941339B - Spherical silicon dioxide catalyst for wastewater ozone catalytic oxidation and preparation method and application thereof - Google Patents
Spherical silicon dioxide catalyst for wastewater ozone catalytic oxidation and preparation method and application thereof Download PDFInfo
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- CN113941339B CN113941339B CN202111130917.XA CN202111130917A CN113941339B CN 113941339 B CN113941339 B CN 113941339B CN 202111130917 A CN202111130917 A CN 202111130917A CN 113941339 B CN113941339 B CN 113941339B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 56
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 38
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000008188 pellet Substances 0.000 claims description 95
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 239000012798 spherical particle Substances 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000011010 flushing procedure Methods 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- B01J35/40—
-
- B01J35/51—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Abstract
The invention relates to the technical field of catalysts, in particular to a spherical silicon dioxide catalyst for wastewater ozone catalytic oxidation, and a preparation method and application thereof, wherein the preparation method comprises the following steps: ptO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 The NiO and the CuO are prepared into composite catalytic active powder according to a proportion, then the composite catalytic active powder and nitrate or sulfate are prepared into metal salt solution, the metal salt solution is used for soaking the spherical silica skeleton which is baked at high temperature, and then the spherical silica catalyst for the ozone catalytic oxidation of the wastewater is obtained through multiple high-temperature calcination. The catalyst has high catalytic efficiency, improves the ozone utilization rate, further reduces the COD value of the effluent, reduces the residence time, can slow down the attenuation of the catalytic effect of the catalyst, and has longer service life, thereby reducing the economic cost of a sewage treatment plant as a whole.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a spherical silicon dioxide catalyst for wastewater ozone catalytic oxidation, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
With the rapid development of industry, the amount and variety of industrial wastewater are rapidly increased, and the pollution to water is also increasingly serious, thereby threatening the health of people. The organic matter concentration of the high-difficulty waste water is high, the COD is generally more than 2000mg/L, some waste water is even more than tens of thousands or even hundreds of thousands mg/L, but the BOD is lower, the ratio of BOD to COD of many waste water is less than 0.3, the biodegradability is poor, and the waste water is difficult to treat by the traditional biochemical method.
Most of the high-difficulty waste water has complex components, high sulfide, nitride and heavy metal contents, toxic substances are contained in the waste water, and the organic matters in the waste water are mostly heterocyclic compounds and aromatic compounds.
In recent years, the diversified development of industrial wastewater treatment technology and the appearance of widely distributed refractory high-concentration organic wastewater make a great deal of application and research of ozone treatment technology in water treatment become reality. Summarizing the advantages of ozone oxidation: secondary pollution is not caused; after ozone is dissolved in water, the resulting oxidation-reduction potential is very high, the oxidation capacity is very strong, and is inferior to fluorine. When ozone with the same amount is used, hydroxyl free radicals are generated in the presence of a catalyst, and the hydroxyl free radicals are used as the oxidant with the strongest oxidizing ability in water, so that various organic matters can be easily oxidized. And no odor and sludge are generated.
The inventor finds that the prior art still has the defects that the catalytic effect is not good enough, and the catalyst efficiency is greatly reduced when the catalyst runs continuously for a long time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a spherical silicon dioxide catalyst for wastewater ozone catalytic oxidation, and a preparation method and application thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater, the method comprising:
PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 Preparing NiO and CuO into composite catalytic active powder according to a proportion, preparing a metal salt solution with nitrate or sulfate, soaking a spherical silicon dioxide skeleton which is baked at high temperature in the metal salt solution, and calcining at high temperature for multiple times to obtain the catalyst for ozone catalytic oxidation of wastewaterSpherical silica catalysts.
In a second aspect of the invention, there is provided a spherical silica catalyst for wastewater ozone catalytic oxidation prepared by the preparation method of the spherical silica catalyst for wastewater ozone catalytic oxidation of the first aspect.
In a third aspect of the invention, there is provided the use of the spherical silica catalyst for the ozone catalytic oxidation of wastewater of the second aspect in the catalytic ozone oxidation of wastewater.
The specific embodiment of the invention has the following beneficial effects:
the catalyst has high catalytic efficiency, improves the ozone utilization rate, further reduces the COD value of the effluent, reduces the residence time, can slow down the attenuation of the catalytic effect of the catalyst, and has longer service life, thereby reducing the economic cost of a sewage treatment plant as a whole;
the prepared catalyst has a skeleton of 2-6mm silica spheres, and a large specific surface area of 500m 2 And/g, the reaction contact area is increased, the contact of the catalyst active ingredient and water is facilitated, and the catalyst effect can be better exerted; the content of active ingredients on the framework is also improved by repeated high-temperature roasting;
pt, mn, CO, ti, fe, ni, cu seven metal catalysts are matched with each other, so that the ozone utilization rate can be remarkably improved in the catalytic reaction of the ozone oxidation reaction, and the COD value of effluent water can be further reduced.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In one embodiment of the invention, a preparation method of a spherical silica catalyst for wastewater ozone catalytic oxidation is provided, and the method comprises the following steps:
PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 The NiO and the CuO are prepared into composite catalytic active powder according to a proportion, then the composite catalytic active powder and nitrate or sulfate are prepared into metal salt solution, the metal salt solution is used for soaking the spherical silica skeleton which is baked at high temperature, and then the spherical silica catalyst for the ozone catalytic oxidation of the wastewater is obtained through multiple high-temperature calcination.
Specifically, the preparation method comprises the following steps:
(1) Taking silicon dioxide to make spherical particles, and firing at high temperature to obtain silicon dioxide spherical particles;
(2) Soaking the silica spheres obtained in the step (1) in nitric acid or hydrochloric acid solution, washing to neutrality, and drying to obtain a silica sphere skeleton;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 The NiO and the CuO are prepared into composite catalytic active powder according to a certain proportion, and are prepared into metal salt solution with nitric acid or sulfuric acid;
(4) Soaking the silica spheres in a metal salt solution for 5-15h;
(5) Drying the impregnated silica pellets;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 500-800 ℃ for 2-6 hours;
(7) Taking out the baked silica pellets, and cooling at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) at least twice to obtain the final product catalyst.
In one or more ofIn various embodiments, the silica spheres in step (1) have a diameter of 2-6mm; the specific surface area is very large and can reach 500m 2 And/g, the reaction contact area is increased, the contact of the catalyst active ingredient and water is facilitated, and the catalyst effect can be better exerted;
in one or more embodiments, firing in step (1) at 700-900 ℃ for 4-5 hours; the high-temperature firing can activate the catalyst framework;
in one or more embodiments, the mass concentration of nitric acid or hydrochloric acid solution in step (2) is 3-5%;
in one or more embodiments, the concentration of the metal salt solution in step (3) is from 0.2 to 0.6mol/L;
in one or more embodiments, ptO in step (3) 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 The ratio of (1) is 0.5-1%, 5-7%, 3.5-4%, 1-2%, 1.2-2%, 4.5-5.5%, 81-82%; the active components of the catalyst are various transition metals, and the transition metals have d orbitals or empty d orbitals, so that empty orbitals can be provided to serve as electrophiles or lone pair electrons can be provided to serve as nucleophiles in chemical reactions, thereby forming intermediate products and OH - The reaction activation energy is reduced, the oxidation capability is enhanced, the reaction is promoted, various transition metals in the application participate in catalysis together, ozone is catalyzed to oxidize organic matters more favorably, the ozone utilization rate is improved, and the catalysis efficiency is further improved, so that the COD index of the effluent is lower.
In one or more embodiments, the drying temperature in step (5) is 100 ℃ ± 5 ℃.
The skeleton of the catalyst prepared in the embodiment of the invention is 2-6mm of silica spheres, the specific surface area is large and can reach 500m 2 And/g, the reaction contact area is increased, the contact of the catalyst active ingredient and water is facilitated, and the catalyst effect can be better exerted; the content of active components on the framework is increased by repeated high-temperature roasting, and the active components of the catalyst are multiple transition metalsThe synergy between the two is more beneficial to catalyzing ozone oxidation.
In one embodiment of the invention, a spherical silica catalyst for wastewater ozone catalytic oxidation prepared by the preparation method of the spherical silica catalyst for wastewater ozone catalytic oxidation is provided.
In one embodiment of the invention, the application of the spherical silica catalyst for wastewater ozone catalytic oxidation in catalyzing wastewater ozone oxidation is provided.
The invention is further illustrated and described below in connection with specific examples.
Example 1
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in nitric acid or hydrochloric acid solution with the mass concentration of 5% for 8min, then flushing with neutral water to a pH value of 7, and then drying with hot air at 90 ℃ to obtain a silica pellet skeleton;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L from composite catalytic active powder and sulfuric acid according to the proportion of 0.5%, 6%, 4%, 1.5%, 1.2%, 5% and 81.8%;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
After the catalyst is used for catalyzing ozone to treat wastewater, the COD value of the chemical oxygen demand in the wastewater is reduced from 314mg/L to 69mg/L, so that the latest emission standard requirement of the local river basin environment is met; the pilot plant runs continuously for more than 40 days, the COD value of the wastewater discharge is always kept stable, and the pilot plant test requirement is met.
Example 2
(1) Taking silicon dioxide spherical particles with the diameter of 6mm, airing, and firing at 700 ℃ for about 5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 3% for 6min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at the temperature of 95 ℃ to obtain a silica pellet framework;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution by compounding catalytic active powder and nitric acid or sulfuric acid according to the proportion of 1%, 6%, 3.5%, 1.5%, 2%, 5% and 81%, wherein the concentration is 0.6mol/L;
(4) Immersing the silica pellets in a metal salt solution for 15 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 105 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 800 ℃ for 4 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 10 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Example 3
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L from composite catalytic active powder and nitric acid according to the proportion of 0.6%, 6.5%, 4%, 1.5%, 4.5% and 81.2%;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Example 4
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L from composite catalytic active powder and nitric acid according to the proportion of 0.8%, 6.5%, 3.5%, 1.5%, 1.4%, 5% and 81.4%;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Example 5
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L from composite catalytic active powder and nitric acid according to the proportion of 0.4%, 5.5%, 3.5%, 2%, 1.6%, 5% and 82%;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Comparative example 1
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) MnO is added to 2 、CO 3 O 4 、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L according to the proportion of 6.2%, 4.1%, 5.2% and 84.5% by compounding catalytic active powder and nitric acid for standby;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Comparative example 2
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) MnO is added to 2 、CO 3 O 4 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L according to the proportion of 6.2%, 3.6%, 2.1%, 5.1% and 83% by compounding catalytic active powder and nitric acid for standby;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Comparative example 3
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) MnO is added to 2 、NiO、CuO、Fe 2 O 3 Preparing a metal salt solution with the concentration of 0.5mol/L for standby according to the proportion of 6.9%, 1.6%, 4.8% and 86.7% by compounding catalytic active powder and nitric acid;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Comparative example 4
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) MnO is added to 2 、CO 3 O 4 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L according to the proportion of 6.7%, 3.6%, 1.4%, 5.1% and 83.2% by compounding catalytic active powder and nitric acid for standby;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
Comparative example 5
(1) Taking silicon dioxide spherical particles with the diameter of 4mm, airing, and firing at 800 ℃ for 4.5 hours to obtain silicon dioxide spherical particles;
(2) Soaking the silica pellets obtained in the step (1) in a nitric acid solution with the mass concentration of 5% for 8min, then flushing the silica pellets with neutral water to a pH value of 7, and then drying the silica pellets with hot air at 90 ℃ to obtain a silica pellet framework;
(3) MnO is added to 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 Preparing metal salt solution with concentration of 0.5mol/L according to the proportion of 5.5%, 3.5%, 2%, 1.6%, 5% and 82.4% by compounding catalytic active powder and nitric acid for standby;
(4) Immersing the silica pellets in a metal salt solution for 10 hours;
(5) Draining the impregnated silica pellets, airing at room temperature, and then drying for 3 hours in an environment of 100 ℃;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 600 ℃ for 5 hours;
(7) Taking out the baked silica pellets, and cooling the silica pellets for 8 hours at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) twice to obtain the final product catalyst.
The COD value of the obtained low-concentration COD water sample is 314mg/L, and after the catalyst of the examples and the comparative example is used for ozone catalytic oxidation, the respective residual COD values are shown in the following table: (Unit: mg/L)
Experimental data show that the removal rate of COD by ozone catalytic oxidation of the catalyst of the comparative example is about 30% -50%, and the removal rate of COD by ozone catalytic oxidation of the catalyst prepared by the embodiment of the invention can reach 72% on average, so that the catalytic effect of the catalyst of the comparative example is obviously improved. In addition, the catalyst of the embodiment of the invention runs for more than 40 days in pilot scale, and the COD value of wastewater discharge is always stable, which indicates that the service life of the catalyst is longer.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the spherical silica catalyst for wastewater ozone catalytic oxidation is characterized by comprising the following steps of:
PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 Preparing NiO and CuO into composite catalytic active powder according to a proportion, preparing a metal salt solution with nitric acid or sulfuric acid, soaking a spherical silica skeleton which is baked at high temperature in the metal salt solution, and calcining at high temperature for multiple times to obtain a spherical silica catalyst for catalytic oxidation of wastewater ozone;
the PtO 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 The ratio of (1) is 0.5% -1%, 5% -7%, 3.5% -4%, 1% -2%, 1.2% -2%, 4.5% -5.5% and 81% -82%.
2. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 1, wherein the preparation method comprises the steps of:
(1) Taking silicon dioxide to make spherical particles, and firing at high temperature to obtain silicon dioxide spherical particles;
(2) Soaking the silica spheres obtained in the step (1) in nitric acid or hydrochloric acid solution, washing to neutrality, and drying to obtain a silica sphere skeleton;
(3) PtO is to 2 、MnO 2 、CO 3 O 4 、TiO 2 、Fe 2 O 3 The NiO and the CuO are prepared into composite catalytic active powder according to a certain proportion, and are prepared into metal salt solution with nitric acid or sulfuric acid;
(4) Soaking the silica spheres in a metal salt solution for 5-15h;
(5) Drying the impregnated silica pellets;
(6) Roasting the dried silica pellets in ammonia gas at a high temperature of 500-800 ℃ for 2-6 hours;
(7) Taking out the baked silica pellets, and cooling at room temperature;
(8) Repeating the steps (4), (5), (6) and (7) at least twice to obtain the final product catalyst.
3. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein the diameter of the silica pellet in the step (1) is 2 to 6mm.
4. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein the firing is performed at 700-900 ℃ for 4-5 hours in step (1).
5. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein the mass concentration of the nitric acid or hydrochloric acid solution in the step (2) is 3 to 5%.
6. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein the concentration of the metal salt solution in the step (3) is 0.2 to 0.6mol/L.
7. The method for producing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein PtO is used in step (3) 2 、MnO 2 、CO 3 O 4 、TiO 2 、NiO、CuO、Fe 2 O 3 The ratio of (1) is 0.5% -1%, 5% -7%, 3.5% -4%, 1% -2%, 1.2% -2%, 4.5% -5.5% and 81% -82%.
8. The method for preparing a spherical silica catalyst for ozone catalytic oxidation of wastewater according to claim 2, wherein the drying temperature in step (5) is 100 ℃ ± 5 ℃.
9. A spherical silica catalyst for use in the ozone catalytic oxidation of wastewater, which is prepared by the method for preparing the spherical silica catalyst for use in the ozone catalytic oxidation of wastewater according to any one of claims 1 to 8.
10. Use of the spherical silica catalyst for wastewater ozone catalytic oxidation according to claim 9 for catalyzing wastewater ozone oxidation.
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| CN106552644A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Difficult biochemical waste water ozone catalyst and preparation method thereof |
| CN109794260A (en) * | 2019-02-22 | 2019-05-24 | 上海电气集团股份有限公司 | A kind of preparation method and ozone oxidation catalyst of ozone oxidation catalyst |
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| CN106552644A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Difficult biochemical waste water ozone catalyst and preparation method thereof |
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