CN116037116A - Fenton sludge magnetic iron-based catalyst and preparation method and application thereof - Google Patents
Fenton sludge magnetic iron-based catalyst and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000010802 sludge Substances 0.000 title claims abstract description 99
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 41
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000003763 carbonization Methods 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The invention discloses a Fenton sludge magnetic iron-based catalyst and a preparation method and application thereof, and the preparation method comprises the following steps: mixing Fenton sludge and organic sludge in proportion, and crushing to obtain organic iron sludge, wherein the mass ratio of ferric oxide to organic matter in the organic iron sludge is 8-10:1; adding water into the organic iron mud, placing the organic iron mud into a high-pressure reaction kettle, introducing inert gas, and performing hydrothermal carbonization, wherein the hydrothermal carbonization temperature is 150-170 ℃ and the hydrothermal carbonization time is 100-140min; after the hydrothermal carbonization is finished, carrying out solid-liquid separation and drying on the hydrothermal product to obtain dry sludge hydrothermal carbon; and (3) carrying out microwave heating on the dry sludge hydrothermal carbon in an inert atmosphere, stopping microwave heating when the temperature is raised to 500-600 ℃ at 110-130 ℃ per minute, naturally cooling and drying to obtain the magnetic iron-based catalyst.
Description
Technical Field
The invention belongs to the technical field of solid waste utilization, and particularly relates to a Fenton sludge magnetic iron-based catalyst and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The Fenton technology is a high-efficiency and economic wastewater treatment technology and is widely applied to the industries of textile, pharmacy, chemical industry and the like. The sludge produced by Fenton's process for treating wastewater is called Fenton's sludge, which contains a large amount of iron ions, organics and heavy metals. At present, the treatment method of Fenton sludge in China mainly comprises landfill, incineration, cement manufacture and the like, so that a great amount of iron resources are wasted, and secondary pollution is easily caused.
The microwave heating has the advantages of high heating efficiency, body heating, simple equipment, quick start and stop and the like, and is a common mode for sludge disposal. However, microwave heating is selective, and the microwave heating characteristics of a substance in a microwave field depend on the dielectric loss coefficient thereof. The microwave heating characteristics of ferric oxide and macromolecular organic matters contained in Fenton sludge are poor, and the defects of slow heating, low efficiency and the like exist when microwave heating is directly adopted.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a Fenton sludge magnetic iron-based catalyst and a preparation method and application thereof.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a Fenton sludge magnetic iron-based catalyst, which comprises the following steps:
mixing Fenton sludge and organic sludge in proportion, and crushing to obtain organic iron sludge, wherein the mass ratio of ferric oxide to organic matter in the organic iron sludge is 8-10:1;
adding water into the organic iron mud, placing the organic iron mud into a high-pressure reaction kettle, introducing inert gas, and performing hydrothermal carbonization, wherein the hydrothermal carbonization temperature is 150-170 ℃ and the hydrothermal carbonization time is 100-140min; after the hydrothermal carbonization is finished, carrying out solid-liquid separation and drying on the hydrothermal product to obtain dry sludge hydrothermal carbon;
and (3) carrying out microwave heating on the dry sludge hydrothermal carbon in an inert atmosphere, stopping microwave heating when the temperature is raised to 500-600 ℃ at 110-130 ℃ per minute, naturally cooling and drying to obtain the magnetic iron-based catalyst.
The inventor finds that the hydrothermal carbonization is carried out in an inert environment, organic matters in Fenton sludge can be subjected to pre-pyrolysis to generate partial carbon, and the carbon is utilized to partially reduce ferric oxide in Fenton sludge into ferroferric oxide with good microwave heating property, but the content of the organic matters in Fenton sludge is limited, so that the ferric oxide in the sludge is difficult to fully reduce, the microwave active sites in a sludge matrix are fewer, and the heavy metal in Fenton sludge is difficult to be cured in situ.
When organic sludge is added into Fenton sludge, the organic content in the organic sludge is high, and part of the organic matters are pre-cracked in the hydrothermal carbonization process, so that on one hand, the pre-cracked product can reduce ferric oxide in the Fenton sludge and promote the generation of ferroferric oxide; on the other hand, the modified activated carbon can be used as an active site, is beneficial to improving the microwave heating characteristic of the sludge mixture, and is further beneficial to realizing in-situ solidification of heavy metals in Fenton sludge. In the third aspect, the organic matter content in the organic sludge is high, and after hydrothermal pre-pyrolysis and microwave further pyrolysis, the specific surface area of the catalyst is improved, and the catalytic performance of the catalyst is improved (the catalytic performance of the catalyst is the result of double functions of adsorption performance and catalytic performance).
The inventor finds that when the temperature of the hydrothermal reaction is higher, the pore diameter structure of a solid product is unstable and is easy to collapse, so that the specific surface area is reduced sharply, in addition, the higher hydrothermal reaction temperature enables iron oxide to be reduced to be ferroferric oxide excessively, so that the microwave heating stage is difficult to control and partial iron simple substance is generated, on one hand, the iron simple substance basically has no catalytic performance, the excessive generation of the iron simple substance reduces the content of active ingredients in the catalyst, and the catalytic performance of the catalyst is reduced to a certain extent; on the other hand, the generated iron simple substance is easy to agglomerate, so that the specific surface area of the catalyst is obviously reduced, and the catalytic performance of the catalyst is further reduced.
Further experiments show that when the hydrothermal reaction temperature is about 165 ℃, the pre-cracking process of the organic matters can be controlled, and the generation process of the ferroferric oxide can be controlled, so that the temperature of the subsequent microwave process is controllable, and the reaction of the microwave process is controllable.
According to the invention, the addition amount of the organic sludge is controlled to be small, carbon formed in the hydrothermal carbonization and microwave pyrolysis processes is mainly used for reducing ferric oxide into ferric oxide, excessive reduction of ferric oxide into iron simple substance is avoided, in addition, the processes of forming carbon through pyrolysis of organic matters (carbon generation, namely microwave active site formation) and reducing ferric oxide into ferric oxide (carbon consumption and ferric oxide generation) exist in the microwave treatment process, and the addition amount of the organic sludge is regulated to ensure that the carbon and the ferric oxide are in a relatively balanced state in the whole sludge system in the microwave treatment process, so that the microwave treatment process is always in a temperature controllable state, and the generation of the iron simple substance due to the uncontrolled and severe reaction of the temperature is avoided.
In addition, the inventor explores the microwave heating procedure, when the heating speed is 110-130 ℃/min, the temperature of the mixed sludge can be quickly heated, so that the in-situ solidification of heavy metals is realized, and when the temperature is raised to 500-600 ℃, the heating is stopped, and in the process, the microwave treatment time is shorter, and the proper reduction of ferric oxide in the sludge can be effectively controlled, so that the excessive reduction into iron simple substance is avoided.
Finally, the hydrothermal carbonization reaction is a high-pressure reaction which is carried out in a reaction kettle, so that the oxidation-reduction reaction can be promoted, and the temperature required for cracking organic matters is reduced. In addition, the hydrothermal carbonization method is used for treating sludge without pre-dewatering, and the dewatering property of a solid product is enhanced after the hydrothermal reaction, the quality is reduced, and the comprehensive dewatering energy consumption is reduced.
In some embodiments, the Fenton sludge has a water content of 30% -80%, an iron oxide content of 40% -65%, and% by mass.
In some embodiments, the water content of the organic sludge is 30% -80%, the organic content is 30% -50%, and the% is mass%. The organic sludge comprises domestic sludge, food processing sludge, tanning sludge, papermaking sludge, printing and dyeing sludge and petrochemical sludge.
In some embodiments, the mass ratio of the organic iron sludge to water is 1:4-6.
Preferably, the mass ratio of the ferric oxide to the organic matters in the organic iron mud is 8.5-9.5:1.
In some embodiments, the rate of temperature rise during hydrothermal carbonization is 3-7deg.C/min.
Preferably, the hydrothermal carbonization temperature is 163-167 ℃, and the hydrothermal carbonization time is 110-130min.
Preferably, stirring is continued during the hydrothermal carbonization.
In some embodiments, microwave heating is stopped when the temperature is raised to 520-570 ℃ at 115-125 ℃/min, naturally cooled and dried.
In a second aspect, the invention provides a Fenton sludge magnetic iron-based catalyst prepared by the preparation method.
In a third aspect, the invention provides an application of the Fenton sludge magnetic iron-based catalyst in toluene catalytic oxidation.
In a fourth aspect, the invention provides an application of the Fenton sludge magnetic iron-based catalyst in adsorbing pentavalent arsenic in a solution.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the ferric oxide is partially reduced into the ferroferric oxide with good microwave heating characteristics by utilizing a hydrothermal carbonization method, macromolecular organic matters are pre-cracked, ferroferric oxide particles and pre-cracked carbon particles generated by the hydrothermal carbonization are dispersed in a sludge matrix, a large number of uniformly dispersed microwave active sites are formed, and the problem of poor Fenton sludge microwave heating characteristics is solved. When the sludge is heated by microwaves, local high temperature is formed near the microwave active site, so that heavy metals in the sludge are solidified in situ. By adopting the mode, the leaching of heavy metals can be effectively prevented when the product is used.
By controlling the temperature of the hydrothermal carbonization reaction and the ratio of ferric oxide to organic matters in the organic iron mud, the phenomenon that the temperature rising characteristic of microwaves is poor or thermal runaway is generated in the microwave heating process is avoided to generate an iron simple substance. In addition, the microwave heating ensures that the pore structure of the solid product after the hydrothermal carbonization reaction is more developed and more stable.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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 invention belongs.
The invention is further illustrated below with reference to examples.
Example 1:
mixing 50g of dehydrated Fenton sludge with the water content of 56.6wt% and the iron oxide content of 56.5wt% with 8g of dehydrated organic sludge with the water content of 59.6wt% and the organic matter content of 41.1wt% and crushing to obtain organic iron sludge, wherein the mass ratio of iron oxide to organic iron of the organic iron sludge is measured to be 8.9:1.
Mixing the organic iron mud and water in a mass ratio of 1:5, placing the mixture in a high-pressure reaction kettle, sealing, introducing nitrogen, performing hydrothermal carbonization reaction, continuously stirring the mixture during the period, wherein the stirring speed is 60rpm, the heating rate is 5 ℃/min, the target temperature is 165 ℃, maintaining the target temperature for 120min, naturally cooling the mixture, and performing solid-liquid separation and drying on the product to obtain the dry sludge hydrothermal carbon.
And (3) placing the dry sludge hydrothermal carbon into a microwave reactor, introducing nitrogen into the reactor, heating by microwaves, stopping when the measured target temperature is 550 ℃, naturally cooling to room temperature, and drying to obtain the magnetic iron-based catalyst. The specific surface area of the magnetic iron-based catalyst was found to be 263m 2 Per g, the saturation magnetization is 12.47emu/g.
Example 2:
mixing 50g of dehydrated Fenton sludge with the water content of 56.6wt% and the iron oxide content of 56.5wt% with 6g of dehydrated organic sludge with the water content of 57.1wt% and the organic matter content of 48.3wt% and crushing to obtain organic iron sludge, wherein the mass ratio of the iron oxide to the organic iron sludge is 9.5:1.
Mixing the organic iron mud and water in a mass ratio of 1:5, placing the mixture in a high-pressure reaction kettle, sealing, introducing nitrogen, performing hydrothermal carbonization reaction, continuously stirring the mixture during the period, wherein the stirring speed is 60rpm, the heating rate is 5 ℃/min, the target temperature is 170 ℃, maintaining the temperature at the target temperature for 120min, naturally cooling the mixture, and performing solid-liquid separation and drying on the product to obtain the dry sludge hydrothermal carbon.
And (3) placing the dry sludge hydrothermal carbon into a microwave reactor, introducing nitrogen into the reactor, heating by microwaves, stopping when the measured target temperature is 580 ℃, naturally cooling to room temperature, and drying to obtain the magnetic iron-based catalyst. The specific surface area of the magnetic iron-based catalyst was measured to be 237m 2 Per g, the saturation magnetization is 11.89emu/g.
Example 3:
mixing 50g of dehydrated Fenton sludge with the water content of 56.6wt% and the iron oxide content of 56.5wt% with 10g of dehydrated organic sludge with the water content of 63.5wt% and the organic matter content of 38.9wt% and crushing to obtain organic iron sludge, wherein the mass ratio of the iron oxide to the organic iron sludge is 8.3:1.
Mixing the organic iron mud and water in a mass ratio of 1:5, placing the mixture in a high-pressure reaction kettle, sealing, introducing nitrogen, performing hydrothermal carbonization reaction, continuously stirring the mixture during the period, wherein the stirring speed is 60rpm, the heating rate is 5 ℃/min, the target temperature is 150 ℃, maintaining the target temperature for 120min, naturally cooling the mixture, and performing solid-liquid separation and drying on the product to obtain the dry sludge hydrothermal carbon.
And (3) placing the dry sludge hydrothermal carbon into a microwave reactor, introducing nitrogen into the reactor, heating by microwaves, stopping when the temperature rise rate is 125 ℃/min and the measured target temperature is 510 ℃, naturally cooling to room temperature, and drying to obtain the magnetic iron-based catalyst. The specific surface area of the magnetic iron-based catalyst was found to be 209m 2 Per g, the saturation magnetization is 10.73emu/g.
Comparative example 1:
the differences from example 1 are: the mass of the added organic sludge is 7g, and the mass ratio of ferric oxide to organic of the organic iron sludge is 10.2:1. Otherwise, the same as in example 1 was used. The specific surface area of the magnetic iron-based catalyst is 135m 2 /g, saturation magnetization of 7.29emu/g.
Comparative example 2:
the differences from example 1 are: the mass of the added organic sludge is 9g, and the mass ratio of ferric oxide to organic of the organic iron sludge is 7.9:1. Otherwise, the same as in example 1 was used. The prepared magnetic iron-based catalyst has a specific surface area of 53m 2 Per g, the saturation magnetization is 9.73emu/g.
Comparative example 3:
the difference from example 1 was that the target temperature for the hydrothermal carbonization reaction was 145℃and the other was the same as in example 1. The magnetic iron-based catalystSpecific surface area of 93m 2 Per g, the saturation magnetization is 2.76emu/g.
Comparative example 4:
the difference from example 1 was that the target temperature for the hydrothermal carbonization reaction was 175℃and the other was the same as in example 1. The specific surface area of the magnetic iron-based catalyst is 146m 2 Per g, the saturation magnetization is 5.75emu/g.
Comparative example 5:
the difference from example 1 was that the target temperature for microwave heating was 490℃and the other was the same as in example 1. The specific surface area of the magnetic iron-based catalyst is 147m 2 Per g, the saturation magnetization is 4.21emu/g.
Comparative example 6:
the difference from example 1 was that the target temperature for microwave heating was 610℃and the other was the same as in example 1. The specific surface area of the magnetic iron-based catalyst is 37m 2 Per g, the saturation magnetization is 7.96emu/g.
Comparative example 7:
the differences from example 1 are: the heating rate of the microwave heating was 105℃per minute, and the same as in example 1 was repeated. The specific surface area of the magnetic iron-based catalyst is 163m 2 Per g, the saturation magnetization is 9.73emu/g.
Comparative example 8:
the differences from example 1 are: the heating rate of the microwave heating was 135℃per minute, and the same as in example 1 was repeated. The specific surface area of the magnetic iron-based catalyst is 102m 2 Per g, the saturation magnetization is 6.29emu/g.
Test example 1:
the magnetic iron-based catalysts prepared in examples 1 to 3 and comparative examples 1 to 8 were subjected to measurement of toluene catalytic oxidation performance as follows:
placing a magnetic iron-based catalyst in a sample tube in a tube furnace, introducing synthetic air with toluene concentration of 500ppm, and recording the temperature when the toluene degradation rate reaches 90% as T90, wherein the space velocity ratio is 20L/(g.h), the heating rate of the tube furnace is 2 ℃/min, and the toluene concentration of the outlet gas is measured by using a high-precision gas chromatograph. The T90 temperature values for the magnetic iron-based catalysts prepared in examples 1-3 and comparative examples 1-8 are shown in Table 1.
Test example 2:
the magnetic iron-based catalysts prepared in examples 1 to 3 and comparative examples 1 to 8 were subjected to measurement of adsorption performance of pentavalent arsenic in solution, as follows:
preparing 100mL of pentavalent arsenic solution with the concentration of 1mg/L, placing 0.2g of a magnetic iron-based catalyst into the solution, adjusting the pH=7 of the solution by using NaOH and HCl, oscillating for 24 hours at the constant temperature of 25 ℃, taking 5mL of the solution to measure the residual concentration of pentavalent arsenic, and calculating to obtain the adsorption rate. The magnetic iron-based catalysts prepared in examples 1-3 and comparative examples 1-8 were tested for their adsorption rates as shown in Table 1.
After one cycle, the magnetic iron-based catalyst is separated by a magnetic field to complete solid-liquid separation, and the solid-liquid separation is dried and tested repeatedly after washing. After 5 cycles, the magnetic iron-based catalysts prepared in examples 1-3 still maintained a 24h adsorption rate of 75% or more.
Table 1 relevant performance parameters of the magnetic iron-based catalysts prepared in examples and comparative examples
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. A preparation method of a Fenton sludge magnetic iron-based catalyst is characterized by comprising the following steps of: the method comprises the following steps:
mixing Fenton sludge and organic sludge in proportion, and crushing to obtain organic iron sludge, wherein the mass ratio of ferric oxide to organic matter in the organic iron sludge is 8-10:1;
adding water into the organic iron mud, placing the organic iron mud into a high-pressure reaction kettle, introducing inert gas, and performing hydrothermal carbonization, wherein the hydrothermal carbonization temperature is 150-170 ℃ and the hydrothermal carbonization time is 100-140min; after the hydrothermal carbonization is finished, carrying out solid-liquid separation and drying on the hydrothermal product to obtain dry sludge hydrothermal carbon;
and (3) carrying out microwave heating on the dry sludge hydrothermal carbon in an inert atmosphere, stopping microwave heating when the temperature is raised to 500-600 ℃ at 110-130 ℃ per minute, naturally cooling and drying to obtain the magnetic iron-based catalyst.
2. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 1, which is characterized in that: the Fenton sludge has a water content of 30% -80%, an iron oxide content of 40% -65% and a mass percentage.
3. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 1, which is characterized in that: the water content of the organic sludge is 30% -80%, the organic matter content is 30% -50%, and the percentage is mass percent.
4. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 1, which is characterized in that: the mass ratio of the ferric oxide to the organic matters in the organic iron mud is 8.5-9.5:1.
5. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 1, which is characterized in that: the heating rate of the hydrothermal carbonization process is 3-7 ℃/min.
6. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 5, which is characterized in that: the hydrothermal carbonization temperature is 163-167 ℃, and the hydrothermal carbonization time is 110-130min.
7. The method for preparing the Fenton sludge magnetic iron-based catalyst according to claim 1, which is characterized in that: when the microwave heating is carried out, the temperature is raised to 520-570 ℃ at 115-125 ℃/min, the microwave heating is stopped, and the product is naturally cooled and dried.
8. A Fenton sludge magnetic iron-based catalyst, which is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. The use of the Fenton sludge magnetic iron-based catalyst of claim 8 in the catalytic oxidation of toluene.
10. The use of the Fenton sludge magnetic iron-based catalyst of claim 8 to adsorb pentavalent arsenic in solution.
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