CN112316972A - Preparation method and application of mesoporous-microporous ZSM-5-based ozone catalyst - Google Patents
Preparation method and application of mesoporous-microporous ZSM-5-based ozone catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 238000011282 treatment Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000009736 wetting Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- ZDZOTLJHXYCWBA-VCVYQWHSSA-N N-debenzoyl-N-(tert-butoxycarbonyl)-10-deacetyltaxol Chemical compound O([C@H]1[C@H]2[C@@](C([C@H](O)C3=C(C)[C@@H](OC(=O)[C@H](O)[C@@H](NC(=O)OC(C)(C)C)C=4C=CC=CC=4)C[C@]1(O)C3(C)C)=O)(C)[C@@H](O)C[C@H]1OC[C@]12OC(=O)C)C(=O)C1=CC=CC=C1 ZDZOTLJHXYCWBA-VCVYQWHSSA-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960003668 docetaxel Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
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- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a mesoporous and microporous ZSM-5-based ozone catalyst, which comprises the following steps: a. cleaning ZSM-5 powder with deionized water, and performing suction filtration and drying to obtain powder A; b. placing the powder A into a sodium hydroxide solution, treating for 20-40 min under the water bath condition of 50-80 ℃, and then performing suction filtration, washing and drying to obtain powder B; c. dissolving cobalt salt and cerium salt in deionized water to obtain a mixed solution C; d. and mixing the mixed solution C with the powder B, drying after ultrasonic treatment, then placing in a tubular furnace, and roasting at 500-600 ℃ for 5-8 h in a nitrogen atmosphere to obtain the ozone catalyst. The invention greatly improves the removal rate of the phenol-containing wastewater catalytically degraded by ozone and the utilization rate of ozone. The preparation method is simple, the raw materials are cheap and easy to obtain, and the method has a good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a mesoporous and microporous ZSM-5-based ozone catalyst.
Background
China has uneven water resource distribution, obvious continuous water-rich years and dry water years change in the year, and the situation that the east is few in docetaxel and the south is more and the north is less is presented. China is a country short of water resources, and the per capita water resource is 900m3Obviously lower than the limit of water resource shortage (less than or equal to 1000 m)3). The water resource pollution and waste coexist in China, the water pollution phenomenon in China is very serious, and the content of organic matters and heavy metals in industrial wastewater accounts for half of the total pollution amount. The use of a large amount of chemical fertilizers and pesticides in agriculture leads nitrate in rivers to seriously exceed the standard of drinking water, thereby bringing serious harm to production and life, and the economic loss of China caused by water pollution reaches 1000 million yuan every year.
The phenol-containing wastewater has wide pollution range and great harmfulness, and can bring serious harm to human bodies, water bodies, fishes and crops. In the industrial production process, a large amount of phenol-containing wastewater is generated in the production processes of a coking plant, a coal gas generation station, a synthetic phenol plant, a pharmaceutical factory, a synthetic fiber plant and the like. The method is clearly specified in the Integrated wastewater discharge Standard (GB8978-1996) of China, phenolic substances are second pollutants, and the discharge standards of primary wastewater and secondary wastewater are not more than 0.5mg L–1The third level standard should not exceed 2.0mgL–1. Therefore, how to reduce the concentration of phenol in an aqueous environment is a very urgent task.
At present, the following treatments are mainly performed on the waste water containing phenols: recovering high-concentration phenol-containing wastewater by a common solvent extraction method, a steam stripping method and the like; the phenol-containing wastewater with medium and low concentration has low economic value, does not need to be recycled, and is removed by a biological method and an adsorption method. However, the biological method has large operation cost, strict requirements on operation conditions, large occupied area and no application when the treatment requirement is high. The removal of trace phenol is sufficiently ensured as early as a third-stage treatment process by using activated carbon adsorption, but the method is most effective in removing phenols only at a lower pH value. While the chemical oxidation method (ozone catalytic oxidation) is very economical when used as the final treatment after biological dephenolization, and can further improve the removal efficiency of phenol at the lowest operation cost.
At present, research and application aiming at catalytic ozone oxidation (CWOO) catalyst mainly focus on loading single components or mixed components such as Mn, Fe, Cu and the like on activated carbon, carbon nano tube and alpha-Al2O3、γ-Al2O3And zirconia, molecular sieve MCM-41, and the like. For example, document CN109926045A discloses a method for preparing an ozone catalyst, which comprises the following steps: s1, manganese loading: preparing a manganese acetate precursor solution with the mass fraction of Mn of 1-5%, adding the manganese acetate precursor solution into the honeycomb activated carbon after roasting treatment, stirring while dripping, and carrying Mn on the honeycomb activated carbon by isovolumetric impregnation; s2, aging treatment: aging the manganese-loaded activated carbon in the S1 at room temperature for more than or equal to 6 hours; s3, roasting treatment: and drying the aged sample of S2, and roasting at 700-900 ℃ for 3h in an inert gas atmosphere to obtain the ozone catalyst. However, the catalytic effect of the catalyst in the prior art is still not ideal, and the ozone utilization rate is not high, so that the research on the ozone catalyst for efficiently degrading phenol has important significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a mesoporous and microporous ZSM-5-based ozone catalyst, and aims to solve the problems of poor catalytic effect and low ozone utilization rate of the existing ozone catalyst.
The technical scheme adopted by the invention is as follows: a preparation method of a mesoporous and microporous ZSM-5-based ozone catalyst comprises the following steps:
a. cleaning ZSM-5 powder with deionized water, and performing suction filtration and drying to obtain powder A;
b. placing the powder A into a sodium hydroxide solution, treating for 20-40 min under the condition of 50-80 ℃ water bath, then carrying out suction filtration and washing, and placing at 80-100 ℃ for drying for 7-12 h to obtain powder B, wherein the concentration of the sodium hydroxide solution is 0.1-0.5M, and the dosage ratio of the powder A to the sodium hydroxide solution is 1 g: 15-60 mL;
c. dissolving cobalt salt and cerium salt in deionized water to obtain a mixed solution C, wherein the molar ratio of cerium to cobalt in the mixed solution C is 1: 0.2-4, and the mass ratio of the total mass of the cerium salt and the cobalt salt to the deionized water is 1: 5-10;
d. and mixing the mixed solution C with the powder B, drying after ultrasonic treatment, then placing the mixture in a tubular furnace, roasting for 5-8 hours at 500-600 ℃ in a nitrogen atmosphere, and cooling to room temperature after the reaction is finished to obtain the ozone catalyst, wherein the mass ratio of the mixed solution C to the powder B is 2-3.5: 1.
In the step a, the drying is as follows: drying for 7-12 h at 80-100 ℃.
In the step c, the cobalt salt is cobalt nitrate hexahydrate, and the cerium salt is cerous nitrate hexahydrate.
And d, dropwise adding the mixed solution C into the powder B, stirring for 20-30 min, and then carrying out ultrasonic treatment for 20-30 min.
In the step d, the drying is as follows: drying for 7-12 h at 100-120 ℃.
In the step d, the heating rate is 50-60 ℃/h during roasting.
The application of the ozone catalyst prepared by the preparation method in phenol degradation is characterized in that the ozone catalyst is added into phenol-containing wastewater, and ozone is introduced at the same time, wherein the dosage of the catalyst is 0.5-1 g, the dosage of the ozone is 3-5 mg/min, and the reaction time is 30-60 min.
The COD value of the phenol-containing wastewater is 100-300 mg/L.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, the ZSM-5 carrier is treated by the NaOH aqueous alkali, so that the specific surface area of the ZSM-5 can be increased, and meanwhile, the mesopores are introduced into the microporous ZSM-5, so that the further dispersion of active metal is increased due to the existence of the mesopores, the aggregation of the active metal can be effectively reduced, the active sites are increased on the premise of the same metal load, and the utilization rate of the metal is increased. Mesoporous and microporous Ce-Co/ZSM-5 based catalyst, compared with common Al2O3The activity of the carrier loaded Ce-Co is improved by 16.7 percent.
2) According to the invention, the catalytic effect is greatly improved by loading the specific types and specific proportions of active metals, and the catalytic effect is cooperated with the mesoporous-microporous carrier, so that the removal rate of phenol can be remarkably improved and the ozone utilization rate can be greatly improved compared with the active metal with a single component.
3) The preparation method is simple, and the NaOH belongs to a common commercial alkali source, and has a good industrial application prospect. The catalytic performance of the catalyst is greatly improved by simple soaking, stirring and filtering means, and the method is a reliable catalyst preparation process in the field of water treatment.
Drawings
FIG. 1 is a wide angle XRD spectrum (CoO standard card comparison) of ZSM-5 and the samples obtained in example 1.
FIG. 2 shows a wide-angle XRD spectrum (CeO) of ZSM-5 and the samples obtained in example 22Standard card comparison).
FIG. 3 is a scanning electron micrograph of mesoporous ZSM-5.
FIG. 4 is a scanning electron micrograph of a catalyst sample obtained in example 1.
FIG. 5 is a graph of the N of ZSM-5 and ZSM-5 samples treated with different base concentrations2Adsorption-desorption isotherms.
FIG. 6 is a 0-50 nm full pore size distribution plot of a sample treated with ZSM-5 and 0.2M NaOH.
FIG. 7 is a 0-50 nm full aperture distribution plot of samples treated with 0.1M, 0.3M, and 0.5M NaOH.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and reagents used in the examples are commercially available or prepared by methods well known to those of ordinary skill in the art unless otherwise specified. The following examples all achieve the objects of the present invention.
Example 1:
1) 20g of commercial ZSM-5 powder purchased is dispersed in 500mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) 10g of powder A is dissolved in 300mL of 0.2M NaOH solution, stirred for 30min at 65 ℃, filtered, washed and dried at 80 ℃ for 7h to obtain powder B.
3) Take 8.59X 10-4mol hexahydrate cerium nitrate + 3.68X 10-4And dissolving the mol hexahydrate cobalt nitrate into 2.5mL of deionized water to obtain a solution C.
4) Putting 1g of the powder B in a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder B, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain powder D.
5) And (3) placing the powder D in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Ce-Co/ZSM-5. The results of the tests performed on powder B and the catalyst samples are shown in fig. 1, 2, 3, and 4.
6) Preparing 100g of 200mg/L phenol simulated wastewater, adding 0.75g of catalyst Ce-Co/ZSM-5, and introducing ozone (the introduction amount is 3mg/min) simultaneously to perform activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
As can be seen from FIGS. 1 and 2, the XRD spectra show that the crystal structure of ZSM-5 is not destroyed after loading the active components Ce and Co, and the comparison of the standard XRD spectra of CeO2 and CoO can confirm that Ce and Co are indeed the active components of the mesoporous and microporous ZSM-5.
As can be seen from FIGS. 3 and 4, in the electron micrographs, it is shown that the catalyst is uniformly loaded on the crystal on the surface of the ZSM-5, and the method is determined to be capable of well loading the catalyst component to obtain the ZSM-5 catalyst with excellent quality.
Example 2
1) 20g of commercial ZSM-5 powder purchased is dispersed in 500mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) 10g of powder A is dissolved in 300mL of 0.2M NaOH solution, stirred for 30min at 65 ℃, filtered, washed and dried at 80 ℃ for 7h to obtain powder B.
3) Take 4.30 in10-4mol hexahydrate cerium nitrate + 5.52X 10-4And dissolving the mol hexahydrate cobalt nitrate into 2.5mL of deionized water to obtain a solution C.
4) Putting 1g of the powder B in a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder B, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain powder D.
5) And (3) placing the powder D in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Ce-Co/ZSM-5.
6) Preparing 100g of 200mg/L phenol simulated wastewater, adding 0.75g of catalyst Ce-Co/ZSM-5, and introducing ozone (the introduction amount is 3mg/min) simultaneously to perform activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
Example 3
1) 20g of commercial ZSM-5 powder purchased is dispersed in 500mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) Take 8.59X 10-4mol hexahydrate cerium nitrate + 3.68X 10-4And dissolving the mol hexahydrate cobalt nitrate into 2.5mL of deionized water to obtain a solution C.
3) Putting 1g of the powder A into a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder A, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain the powder B.
4) And (3) placing the powder B in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Ce-Co/ZSM-5.
5) Preparing 100g of 200mg/L phenol simulated wastewater, adding 0.75g of catalyst Ce-Co/ZSM-5, and introducing ozone (the introduction amount is 3mg/min) simultaneously to perform activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
Example 4
1) Taking commercial gamma-Al2O3Dispersing 20g of powder in 500mL of deionized water, stirring and washing for 30min, and washing offSoluble impurities. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) Take 8.59X 10-4mol hexahydrate cerium nitrate + 3.68X 10-4And dissolving the mol hexahydrate cobalt nitrate into 2.5mL of deionized water to obtain a solution C.
4) Putting 1g of the powder A into a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder A, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain the powder B.
5) Placing the powder B in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Ce-Co/gamma-Al2O3。
6) Preparing 100g of 200mg/L phenol simulation wastewater, and adding 0.75g of catalyst Ce-Co/gamma-Al2O3And simultaneously introducing ozone (the introduction amount is 3mg/min) for activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
Example 5
1) 20g of commercial ZSM-5 powder purchased is dispersed in 500mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) 10g of powder A is dissolved in 300mL of 0.2M NaOH solution, stirred for 30min at 65 ℃, filtered, washed and dried at 80 ℃ for 7h to obtain powder B.
3) Take 7.37X 10-4And dissolving the mol cerous nitrate hexahydrate in 2.5mL of deionized water to obtain a solution C.
4) Putting 1g of the powder B in a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder B, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain powder D.
5) And (3) placing the powder D in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Ce/ZSM-5.
6) Preparing 100g of 200mg/L phenol simulated wastewater, adding 0.75g of catalyst Ce/ZSM-5, and introducing ozone (the introduction amount is 3mg/min) simultaneously to perform an activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
Example 6
1) 20g of commercial ZSM-5 powder purchased is dispersed in 500mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) 10g of powder A is dissolved in 300mL of 0.2M NaOH solution, stirred for 30min at 65 ℃, filtered, washed and dried at 80 ℃ for 7h to obtain powder B.
3) Take 1.72X 10-3Cobalt nitrate hexahydrate was dissolved in 2.5mL of deionized water to give solution C.
4) Putting 1g of the powder B in a beaker, gradually dripping 2.5mL of the solution C, stirring for 20min after completely wetting the powder B, then carrying out ultrasonic treatment for 20min, standing overnight, drying for 7h at 100 ℃, and cooling to room temperature in a dryer to obtain powder D.
5) And (3) placing the powder D in a tubular heating furnace, raising the temperature to 550 ℃ at a constant speed for 5h under the protection of nitrogen atmosphere, roasting at a constant temperature for 6h, and then naturally cooling to room temperature to obtain the catalyst Co/ZSM-5.
6) Preparing 100g of 200mg/L phenol simulated wastewater, adding 0.75g of catalyst Co/ZSM-5, and introducing ozone (the introduction amount is 3mg/min) simultaneously to perform activity test, wherein the reaction time is 30 min. The test results are shown in table 1.
Table 1:
| examples | Catalyst and process for preparing same | Phenol removal rate% | COD removal rate% |
| Blank group | Pure ozone | 80.91％ | 32.91％ |
| Example 1 | Ce-Co/ZSM-5 | 98.31％ | 58.55％ |
| Example 2 | Ce-Co/ZSM-5 | 97.18％ | 57.83％ |
| Example 3 | Ce-Co/ZSM-5 (unmodified) | 91.22％ | 51.09％ |
| Example 4 | Ce-Co/γ-Al2O3 | 89.97％ | 46.89％ |
| Example 5 | Ce/ZSM-5 | 90.81％ | 49.37％ |
| Example 6 | Co/ZSM-5 | 88.56％ | 43.4％ |
As can be seen from Table 1, the removal rate of phenol and COD of the Ce-Co/ZSM-5 catalyst prepared in the range given by the invention is greatly improved compared with the catalyst prepared by a normal carrier and an unmodified carrier on the market. The removal rate of the catalyst prepared by only using a single metal catalyst component is greatly reduced compared with the removal rate of the composite catalyst prepared in the proportioning range provided by the invention. Therefore, the advantages of the modified ZSM-5 carrier and the composite catalyst in proportion can be embodied.
Example 7
1) 50g of commercial ZSM-5 powder purchased is dispersed in 1200mL of deionized water, stirred and washed for 30min, and soluble impurities are washed away. Suction filtration and drying at 100 ℃ for 12h to obtain powder A.
2) 10g of the powder A washed in the step 1 is dissolved in 300mL of 0.1M, 0.2M, 0.3M and 0.5M NaOH solutions respectively, and stirred for 30min at 65 ℃ to obtain modified ZSM-5 powder.
3) The performance tests of the powder A and the ZSM-5 powder modified by different sodium hydroxide concentrations are respectively carried out, and the results are shown in Table 2 and FIGS. 5 to 7.
Table 2:
as seen from BET data, after the ZSM-5 is treated by alkali, the external specific surface area, the pore volume and the average pore diameter are greatly improved. While the BET surface area increases with increasing treatment concentration. This shows that the ZSM-5 after the alkali treatment is more favorable for the distribution of the active components and can effectively reduce the agglomeration of the active components.
As can be seen from FIG. 6, comparing the full-aperture distribution diagrams of ZSM-5 and 0.2M NaOH-treated ZSM-5 samples, it can be found that, after the NaOH treatment, 8-15 nm mesopores appear in the microporous ZSM-5, and a ZSM-5 molecular sieve in which mesopores and micropores coexist is formed. Meanwhile, the number of mesopores is gradually increased along with the increase of the treatment concentration. The mesoporous and microporous ZSM-5 molecular sieve can be obtained within the scope of the invention.
Claims (8)
1. A preparation method of a mesoporous and microporous ZSM-5-based ozone catalyst is characterized by comprising the following steps:
a. cleaning ZSM-5 powder with deionized water, and performing suction filtration and drying to obtain powder A;
b. placing the powder A into a sodium hydroxide solution, treating for 20-40 min under the condition of 50-80 ℃ water bath, then carrying out suction filtration and washing, and placing at 80-100 ℃ for drying for 7-12 h to obtain powder B, wherein the concentration of the sodium hydroxide solution is 0.1-0.5M, and the dosage ratio of the powder A to the sodium hydroxide solution is 1 g: 15-60 mL;
c. dissolving cobalt salt and cerium salt in deionized water to obtain a mixed solution C, wherein the molar ratio of cerium to cobalt in the mixed solution C is 1: 0.2-4, and the mass ratio of the total mass of the cerium salt and the cobalt salt to the deionized water is 1: 5-10;
d. and mixing the mixed solution C with the powder B, drying after ultrasonic treatment, then placing the mixture in a tubular furnace, roasting for 5-8 hours at 500-600 ℃ in a nitrogen atmosphere, and cooling to room temperature after the reaction is finished to obtain the ozone catalyst, wherein the mass ratio of the mixed solution C to the powder B is 2-3.5: 1.
2. The method of claim 1, wherein the drying step a comprises: drying for 7-12 h at 80-100 ℃.
3. The method of claim 1, wherein in step c, the cobalt salt is cobalt nitrate hexahydrate, and the cerium salt is cerium nitrate hexahydrate.
4. The method for preparing a mesoporous and microporous ZSM-5-based ozone catalyst as claimed in claim 1, wherein in step d, the mixed solution C is added dropwise to the powder B, followed by stirring for 20-30 min and then ultrasonic treatment for 20-30 min.
5. The method of claim 1, wherein the drying step d comprises: drying for 7-12 h at 100-120 ℃.
6. The method for preparing a mesoporous and microporous ZSM-5-based ozone catalyst as claimed in claim 1, wherein in step d, the temperature rise rate during calcination is 50-60 ℃/h.
7. The application of the ozone catalyst prepared by the preparation method of any one of claims 1 to 6 in phenol degradation is characterized in that the ozone catalyst is added into the wastewater containing phenol, and simultaneously ozone is introduced, wherein the dosage of the catalyst is 0.5 to 1g, the dosage of the ozone is 3 to 5mg/min, and the reaction time is 30 to 60 min.
8. The use according to claim 7, wherein the phenol-containing wastewater has a COD value of 100 to 300 mg/L.
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|---|---|---|---|---|
| CN113171783A (en) * | 2021-04-21 | 2021-07-27 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307534A (en) * | 2014-10-31 | 2015-01-28 | 天津市联合环保工程设计有限公司 | Preparation method for MnO2-CeO2-CoO/AC ternary supported catalyst for treatment of phenolic wastewater |
| CN105381797A (en) * | 2015-10-16 | 2016-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of catalytic ozonation supported catalyst used for treating sewage and doped with dual rare earth elements |
| CN106256426A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of catalyst for O3 catalytic oxidation and preparation method thereof |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
| CN108654678A (en) * | 2018-05-31 | 2018-10-16 | 上海绿强新材料有限公司 | One type Fenton oxidation catalyst and its application |
| CN108837843A (en) * | 2018-06-26 | 2018-11-20 | 清华大学 | A kind of Bimetallic Zeolite Catalyst and its preparation and application |
| CN111375406A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Ozone catalytic oxidation catalyst and preparation method thereof |
-
2020
- 2020-10-16 CN CN202011110974.7A patent/CN112316972A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104307534A (en) * | 2014-10-31 | 2015-01-28 | 天津市联合环保工程设计有限公司 | Preparation method for MnO2-CeO2-CoO/AC ternary supported catalyst for treatment of phenolic wastewater |
| CN106256426A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of catalyst for O3 catalytic oxidation and preparation method thereof |
| CN105381797A (en) * | 2015-10-16 | 2016-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of catalytic ozonation supported catalyst used for treating sewage and doped with dual rare earth elements |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
| CN108654678A (en) * | 2018-05-31 | 2018-10-16 | 上海绿强新材料有限公司 | One type Fenton oxidation catalyst and its application |
| CN108837843A (en) * | 2018-06-26 | 2018-11-20 | 清华大学 | A kind of Bimetallic Zeolite Catalyst and its preparation and application |
| CN111375406A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Ozone catalytic oxidation catalyst and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| XUE-YU REN ET AL.: ""Catalytic upgrading of pyrolysis vapors from lignite over mono/bimetalloaded mesoporous HZSM-5"", 《FUEL》 * |
| 侯艳君著: "《臭氧金属氧化物催化降解水中有机物的研究》", 30 June 2013, 哈尔滨：黑龙江大学出版社 * |
| 吕树祥等: ""Fe-ZSM-5 分子筛催化剂催化降解高浓度含酚废水"", 《过程工程学报》 * |
| 崔福旭等: ""金属负载ZSM⁃5分子筛催化臭氧化苯酚废水"", 《辽宁石油化工大学学报》 * |
| 王帅军等: ""Fe -Ce /ZSM-5 类Fenton 催化剂降解甲基橙废水的影响因素研究"", 《石油炼制与化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113171783A (en) * | 2021-04-21 | 2021-07-27 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
| CN113171783B (en) * | 2021-04-21 | 2023-03-21 | 中化环境科技工程有限公司 | Microporous honeycomb ozone catalyst and preparation method and application thereof |
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