CN114367281A - Metal supported catalyst and preparation method and application thereof - Google Patents
Metal supported catalyst and preparation method and application thereof Download PDFInfo
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- CN114367281A CN114367281A CN202111683032.2A CN202111683032A CN114367281A CN 114367281 A CN114367281 A CN 114367281A CN 202111683032 A CN202111683032 A CN 202111683032A CN 114367281 A CN114367281 A CN 114367281A
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- filter cake
- graphene oxide
- manganese nitrate
- cerium nitrate
- temperature
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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
- B01J23/16—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a metal supported catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: s101, dispersing graphene oxide in 100ml of deionized water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid; respectively dissolving cerium nitrate and manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under a stirring condition to obtain a mixed solution; s102, dropwise adding the mixed solution into the graphene oxide dispersion liquid under the stirring condition, and after the dropwise adding is finished and the stirring is continued for 0.5-1h, carrying out ultrasonic treatment for 0.5-1 h; s103, filtering to obtain a filter cake, and drying the filter cake; s104, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling to obtain the filter cake. The metal-loaded catalyst can effectively improve the catalytic oxidation efficiency of ozone, improve the utilization rate of ozone, and realize the enrichment and efficient removal of pollutants.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a metal supported catalyst and a preparation method and application thereof.
Background
In recent years, with the rapid development of economy in China, the process of an industrial park is accelerated, the treatment difficulty of various industrial wastewater pollutants is high, the requirement for stable and standard-reaching deep treatment of the tail water of a park sewage plant is increasingly remarkable, and the resource recycling of the tail water pollutants of the industrial park sewage plant is one of important tasks of water environment pollution. Ozone, as a strong oxidant, is increasingly used for the oxidation treatment of pollutants in sewage. In the prior art, ozone is generally directly introduced into sewage, but the introduced ozone has low oxidation efficiency and low utilization rate. How to improve the oxidation efficiency of ozone and then promote its utilization ratio, the removal of more high-efficient realization pollutant is the technological problem that this field needs to solve urgently.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a metal-loaded catalyst which can effectively improve the catalytic oxidation efficiency of ozone, improve the utilization rate of ozone and realize the enrichment and efficient removal of pollutants.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for preparing a metal-supported catalyst, comprising the steps of:
s101, dispersing graphene oxide in 100ml of deionized water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid; respectively dissolving cerium nitrate and manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under a stirring condition to obtain a mixed solution;
s102, dropwise adding the mixed solution into the graphene oxide dispersion liquid under the stirring condition, and after the dropwise adding is finished and the stirring is continued for 0.5-1h, carrying out ultrasonic treatment for 0.5-1 h;
s103, filtering to obtain a filter cake, and drying the filter cake;
s104, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling to obtain the filter cake.
Further, in the step S101, the mass ratio of the sum of the cerium nitrate and the manganese nitrate to the graphene oxide is 5-10: 1.
Further, in the step S101, the mass ratio of the cerium nitrate to the manganese nitrate is 2.5-3: 1.
Further, in the step S101, the stirring speed is 200-300 rpm.
Further, in the step S102, the stirring speed is 500-600 rpm.
Further, in the step S103, a filter membrane with a pore diameter of 0.45um is used for filtration.
Further, in the step S103, the drying temperature is 50-60 ℃, and the drying time is 65-85 h.
Further, in step S104, the specific baking and activating process includes: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 h.
The invention also comprises a metal supported catalyst prepared by adopting the method.
The invention also comprises the application of the metal-loaded catalyst in ozone oxidation treatment of wastewater.
Compared with the prior art, the invention has the beneficial effects that: the metal-loaded catalyst prepared by the invention can effectively improve the catalytic oxidation efficiency of ozone, realizes the enrichment and efficient removal of pollutants, has a stable combination effect, and can prevent heavy metals on the catalyst from being dissolved in water to cause secondary pollution.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The invention discloses a preparing method of metal load catalyst, which comprises the following steps:
a method for preparing a metal-supported catalyst, comprising the steps of:
s101, dispersing graphene oxide in 100ml of deionized water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid; respectively dissolving cerium nitrate and manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under a stirring condition to obtain a mixed solution;
s102, dropwise adding the mixed solution into the graphene oxide dispersion liquid under the stirring condition, and after the dropwise adding is finished and the stirring is continued for 0.5-1h, carrying out ultrasonic treatment for 0.5-1 h;
s103, filtering to obtain a filter cake, and drying the filter cake;
s104, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling to obtain the filter cake.
Further, in the step S101, the mass ratio of the sum of the cerium nitrate and the manganese nitrate to the graphene oxide is 5-10: 1; the mass ratio of the cerium nitrate to the manganese nitrate is 2.5-3: 1; the stirring speed was 200-300 rpm. In the step S102, the stirring speed is 500-600 rpm. In the step S103, filtering by adopting a filter membrane with the aperture of 0.45 um; the drying temperature is 50-60 ℃, and the drying time is 65-85 h. In the step S104, the specific roasting and activating process is as follows: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 h.
The invention also comprises a metal-loaded catalyst prepared by the method.
The metal-loaded catalyst is applied to ozone oxidation treatment of wastewater.
Example 1
Preparation of Metal Supported catalyst C-1
S101, dispersing 10mg of graphene oxide in 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h to obtain a graphene oxide dispersion liquid; respectively dissolving 36.1mg of cerium nitrate and 13.9mg of manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under the stirring condition of 200rpm to obtain a mixed solution;
s102.500rpm stirs and adds the mixed solution into the graphene oxide dispersion liquid, after the addition is finished and the stirring is continued for 0.5h, the ultrasonic treatment is carried out for 1 h;
s103, performing suction filtration by using a filter membrane with the aperture of 0.45um to obtain a filter cake, and drying the filter cake at the drying temperature of 50 ℃ for 85 hours;
s104, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling, wherein the specific roasting and activating process comprises the following steps: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; and maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 hours to obtain the metal supported catalyst C-1.
Example 2
Preparation of Metal Supported catalyst C-2
S201, dispersing 10mg of graphene oxide in 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h to obtain a graphene oxide dispersion liquid; respectively dissolving 43.7mg of cerium nitrate and 16.3mg of manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under the stirring condition of 300rpm to obtain a mixed solution;
s202.500rpm stirs and adds the mixed solution into the graphene oxide dispersion liquid, after the addition is finished and the stirring is continued for 1h, the ultrasonic treatment is carried out for 0.5 h;
s203, performing suction filtration by using a filter membrane with the aperture of 0.45um to obtain a filter cake, and drying the filter cake at the drying temperature of 55 ℃ for 72 hours;
s204, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling, wherein the specific roasting and activating process comprises the following steps: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; and keeping the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 hours to obtain the metal supported catalyst C-2.
Example 3
Preparation of Metal Supported catalyst C-3
S301, dispersing 10mg of graphene oxide in 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h to obtain a graphene oxide dispersion liquid; respectively dissolving 58.9mg of cerium nitrate and 21.1mg of manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under the stirring condition of 300rpm to obtain a mixed solution;
s302.600rpm stirs the condition and adds the mixed solution drop by drop to the graphene oxide dispersion, after dropping and continuing to stir for 1h, ultrasonic treatment is carried out for 1 h;
s303, performing suction filtration by using a filter membrane with the aperture of 0.45um to obtain a filter cake, and drying the filter cake at the drying temperature of 60 ℃ for 65 hours;
s304, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling, wherein the specific roasting and activating process comprises the following steps: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; and maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 hours to obtain the metal supported catalyst C-3.
Example 4
Preparation of Metal Supported catalyst C-4
S401, dispersing 10mg of graphene oxide in 100ml of deionized water, and carrying out ultrasonic treatment for 0.5h to obtain a graphene oxide dispersion liquid; respectively dissolving 75mg of cerium nitrate and 25mg of manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under the stirring condition of 200rpm to obtain a mixed solution;
s402, dropwise adding the mixed solution into the graphene oxide dispersion liquid under the stirring condition of 600rpm, continuously stirring for 1h after dropwise adding, and carrying out ultrasonic treatment for 1 h;
s403, performing suction filtration by using a filter membrane with the aperture of 0.45um to obtain a filter cake, and drying the filter cake at the drying temperature of 55 ℃ for 85 h;
s404, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling, wherein the roasting and activating specific process comprises the following steps: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; and maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 hours to obtain the metal supported catalyst C-4.
Example 5
Comparative example: samples were taken at intervals and the pyridine content in the sample solution was determined by continuously introducing ozone into 200mL of a 20mg/L aqueous pyridine solution.
Respectively taking 5mg of the metal-supported catalyst prepared in the embodiment 1-4 to prepare a sheet structure, respectively putting the sheet structure into 200mL of 20mg/L pyridine aqueous solution, sampling and determining the pyridine content in the sample solution at intervals under the condition of continuously introducing ozone, and measuring the final pyridine content in the solution and the heavy metal content in the solution after 40 min; table 1 is compared with the following data:
TABLE 1 comparison of pyridine aqueous solution treatment data
| Item | Comparative example | C-1 | C-2 | C-3 | C-4 |
| Pyridine concentration (mg/L) in the 5min sample | 18.82 | 16.8 | 17.15 | 17.07 | 17.1 |
| Pyridine concentration (mg/L) in sample at 10min | 16.41 | 12.72 | 12.68 | 12.69 | 11.7 |
| Pyridine concentration (mg/L) in sample at 20min | 13.62 | 9.73 | 9.46 | 9.88 | 9.79 |
| Pyridine concentration (mg/L) in sample 30min | 11.84 | 8.79 | 8.89 | 8.75 | 8.98 |
| Pyridine concentration (mg/L) in sample 40min | 10.75 | 7.58 | 7.65 | 7.49 | 7.88 |
| Concentration of cerium (mg/L) in solution at 40min | / | Not detected out | Not detected out | Not detected out | Not detected out |
| Manganese concentration (mg/L) in solution at 40min | / | Not detected out | Not detected out | Not detected out | Not detected out |
From the above table 1, the metal-supported catalyst prepared by the invention can effectively improve the catalytic oxidation efficiency of ozone, realize the enrichment and efficient removal of pollutants, and the supported catalyst has a stable combination effect, and heavy metals on the catalyst cannot be dissolved in water to cause secondary pollution.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (10)
1. A method for preparing a metal-supported catalyst, comprising the steps of:
s101, dispersing graphene oxide in 100ml of deionized water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid; respectively dissolving cerium nitrate and manganese nitrate in 100ml of deionized water to prepare a cerium nitrate solution and a manganese nitrate solution; dropwise adding a manganese nitrate solution into a cerium nitrate solution under a stirring condition to obtain a mixed solution;
s102, dropwise adding the mixed solution into the graphene oxide dispersion liquid under the stirring condition, and after the dropwise adding is finished and the stirring is continued for 0.5-1h, carrying out ultrasonic treatment for 0.5-1 h;
s103, filtering to obtain a filter cake, and drying the filter cake;
s104, roasting and activating the dried filter cake under a vacuum condition, and then naturally cooling to obtain the filter cake.
2. The method according to claim 1, wherein in the step S101, a mass ratio of the sum of the cerium nitrate and the manganese nitrate to the graphene oxide is 5-10: 1.
3. The method according to claim 2, wherein in step S101, the mass ratio of cerium nitrate to manganese nitrate is 2.5-3: 1.
4. The method as set forth in claim 1, wherein the stirring speed in step S101 is 200-300 rpm.
5. The method as set forth in claim 1, wherein the stirring speed in step S102 is 500-600 rpm.
6. The method according to claim 1, wherein in step S103, the filtration is performed by suction filtration using a 0.45um pore size filter.
7. The method of claim 1, wherein in step S103, the drying temperature is 50-60 ℃ and the drying time is 65-85 h.
8. The preparation method according to claim 1, wherein in the step S104, the specific roasting and activating process is as follows: the heating rate is 0.5 ℃/min, and after the temperature is increased from room temperature to 90 ℃, the temperature is kept for 4 h; maintaining the heating rate at 0.5 ℃/min, continuously heating to 400 ℃, and keeping the temperature for 4 h.
9. A metal supported catalyst prepared by the method of any one of claims 1 to 8.
10. Use of the metal-supported catalyst of claim 9 in ozone oxidation treatment of wastewater.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759277A (en) * | 2015-03-18 | 2015-07-08 | 华南理工大学 | CeOx-MnOx/graphene low-temperature SCR flue gas denitration catalyst and preparation method thereof |
| CN107744806A (en) * | 2017-10-16 | 2018-03-02 | 燕山大学 | A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition |
| CN108187664A (en) * | 2017-12-27 | 2018-06-22 | 中国矿业大学(北京) | A kind of preparation method of catalytic ozone oxidation catalyst |
| CN110354846A (en) * | 2019-07-31 | 2019-10-22 | 上海应用技术大学 | A kind of preparation method of manganese cerium dopping graphene low temperature SCR denitration catalyst |
| CN111111685A (en) * | 2019-11-28 | 2020-05-08 | 成都理工大学 | Catalyst for removing quinoline in wastewater by catalytic ozonation and preparation method thereof |
| CN111375424A (en) * | 2020-03-26 | 2020-07-07 | 宁夏大学 | Preparation method and application of supported multi-metal oxide catalytic ozonation catalyst |
-
2021
- 2021-12-31 CN CN202111683032.2A patent/CN114367281A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759277A (en) * | 2015-03-18 | 2015-07-08 | 华南理工大学 | CeOx-MnOx/graphene low-temperature SCR flue gas denitration catalyst and preparation method thereof |
| CN107744806A (en) * | 2017-10-16 | 2018-03-02 | 燕山大学 | A kind of preparation method of catalyst using expanded graphite as carrier catalysis ozone decomposition |
| CN108187664A (en) * | 2017-12-27 | 2018-06-22 | 中国矿业大学(北京) | A kind of preparation method of catalytic ozone oxidation catalyst |
| CN110354846A (en) * | 2019-07-31 | 2019-10-22 | 上海应用技术大学 | A kind of preparation method of manganese cerium dopping graphene low temperature SCR denitration catalyst |
| CN111111685A (en) * | 2019-11-28 | 2020-05-08 | 成都理工大学 | Catalyst for removing quinoline in wastewater by catalytic ozonation and preparation method thereof |
| CN111375424A (en) * | 2020-03-26 | 2020-07-07 | 宁夏大学 | Preparation method and application of supported multi-metal oxide catalytic ozonation catalyst |
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