CN116829262A - Heterogeneous catalytic material and preparation method and application thereof - Google Patents
Heterogeneous catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116829262A CN116829262A CN202380009012.8A CN202380009012A CN116829262A CN 116829262 A CN116829262 A CN 116829262A CN 202380009012 A CN202380009012 A CN 202380009012A CN 116829262 A CN116829262 A CN 116829262A
- Authority
- CN
- China
- Prior art keywords
- catalytic material
- heterogeneous catalytic
- temperature
- solution
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010802 sludge Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 3
- 150000002696 manganese Chemical class 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- -1 iron ions Chemical class 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910001437 manganese ion Inorganic materials 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 22
- 238000000197 pyrolysis Methods 0.000 description 19
- 239000000523 sample Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 230000007935 neutral effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a heterogeneous catalytic material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Carrying out acid washing treatment on Fenton sludge to obtain Fenton sludge acid washing suspension, and then adding a magnesium salt solution and a manganese salt solution to obtain a mixed solution; (2) Adding a chelating flocculant and a pH regulator into the mixed solution prepared in the step (1), aging after reaction to obtain an aged solution, carrying out solid-liquid separation on the aged solution, cleaning and drying the obtained filter residues to obtain a catalytic material precursor; (3) Mixing the catalytic material precursor prepared in the step (2) with asphalt, ball-milling, roasting, cooling, cleaning and drying to obtain the heterogeneous catalytic material. The preparation method is simple and low in cost, and the prepared heterogeneous catalytic material is good in catalytic performance, so that the resource utilization rate of Fenton sludge is greatly improved, and the problems of complex process, high cost and the like in the preparation of the iron-based catalyst by using Fenton sludge in the prior art are solved.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a heterogeneous catalytic material, a preparation method and application thereof.
Background
In the process of recycling the retired battery, a large amount of battery wastewater containing organic phosphorus is generated, and the treatment difficulty of the wastewater is increased and the treatment cost is increased due to the existence of the organic phosphorus, so that an economical and feasible method for treating the battery wastewater containing the organic phosphorus is required to be provided. The Fenton method is a high-efficiency sewage treatment technology, and is commonly used in the advanced sewage treatment process due to the characteristics of strong oxidizing property, short reaction time, high degradation efficiency and the like. However, fenton's method has a narrow pH application range and H in practical application due to the existence of the reaction 2 O 2 The utilization rate is lower, the sludge production amount in the reaction process is large, and the Fenton sludge which is rich in iron elements and part of refractory organic matters belongs to dangerous solid waste and cannot be properly treated, so that the large-scale application of the Fenton sludge is limited to a certain extent.
At present, the Fenton sludge treatment method mainly comprises incineration, landfill treatment, solidification treatment and the like, and has great limitation on the treatment modes, and on one hand, the Fenton sludge contains rich iron elements and has high recycling value; on the other hand, fenton sludge is dangerous solid waste, and waste gas, waste residue and waste liquid can be generated in the incineration, landfill and solidification treatment processes, so that secondary pollution is easy to generate, and great potential danger is caused to the environment. Therefore, the search for an economical and efficient Fenton sludge recycling treatment method has become an important point of research in the art.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a heterogeneous catalytic material, a preparation method and application thereof, wherein the heterogeneous catalytic material is prepared based on Fenton sludge, the preparation method fully utilizes a catalytic coupling action mechanism between Fe element and other active metal elements in Fenton sludge to prepare the heterogeneous catalytic material, the preparation method is simple, the cost is low, the prepared heterogeneous catalytic material has good catalytic performance, the resource utilization rate of Fenton sludge is greatly improved, and the problems of complex process, high cost and the like in the preparation of an iron-based catalyst by Fenton sludge in the prior art are solved.
The technical aim of the invention is realized by the following technical scheme:
a method for preparing a heterogeneous catalytic material, comprising the steps of:
(1) Carrying out acid washing treatment on Fenton sludge to obtain Fenton sludge acid washing suspension, and then adding a magnesium salt solution and a manganese salt solution to obtain a mixed solution;
(2) Adding a chelating flocculant and a pH regulator into the mixed solution prepared in the step (1), aging after reaction to obtain an aged solution, carrying out solid-liquid separation on the aged solution, cleaning and drying the obtained filter residues to obtain a catalytic material precursor;
(3) Mixing the catalytic material precursor prepared in the step (2) with asphalt, ball-milling, roasting, cooling, cleaning and drying to obtain the heterogeneous catalytic material.
Preferably, in the step (1), before the Fenton sludge is subjected to the pickling treatment, the Fenton sludge is further subjected to the drying, crushing and sieving treatment.
Preferably, in the step (1), the pickling treatment means that the Fenton sludge is mixed with an acid solution and then stirred in a constant-temperature water bath.
Preferably, in the step (1), the concentration of the acid liquor is 1% -5%, and the volume ratio of the Fenton sludge to the acid liquor is 1: (5-15) mixing.
Further preferably, in the step (1), the concentration of the acid liquor is 2% -3%, and the volume ratio of the Fenton sludge to the acid liquor is 1: (9-10) mixing.
Preferably, in the step (1), the temperature of the constant-temperature water bath is 50-80 ℃, and the stirring time during the constant-temperature water bath is 0.5-2h.
Further preferably, in the step (1), the temperature of the constant-temperature water bath is 60-70 ℃, and the stirring time during the constant-temperature water bath is 1-1.5h.
Preferably, the acid liquid is at least one of sulfuric acid and hydrochloric acid.
Preferably, in the step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1: (0.8-3): (0.8-1.2).
Further preferably, in step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1: (1-2): 1.
preferably, in the step (2), the chelating flocculant is at least one of dithiocarboxylated methylol polyacrylamide, dithiocarboxylated sulfomethyl polyacrylamide and dithiocarboxylated aminomethyl polyacrylamide.
Further preferably, in step (2), the chelating flocculant is dithiocarboxylated aminomethyl polyacrylamide.
Preferably, in the step (2), the pH regulator is ammonia water with a mass fraction of 5% -10%.
Further preferably, in the step (2), the pH adjuster is ammonia water with a mass fraction of 5% -7%.
Preferably, in step (2), the temperature of the reaction is 50-70 ℃.
Further preferably, in step (2), the temperature of the reaction is 55-65 ℃.
Preferably, in the step (2), the chelating flocculant and the pH regulator are added dropwise, and after the pH in the mixed solution is stabilized between 9.8 and 10.5, the mixed solution is stirred continuously for 2 to 4 hours, and then is kept stand and aged for 10 to 15 hours to obtain the aged solution.
Further preferably, in the step (2), the chelating flocculant and the pH adjuster are added dropwise, and after the pH in the mixed solution is stabilized between 9.8 and 10, the mixed solution is stirred continuously for 3 hours, and then is kept stand and aged for 12 hours to obtain the aged solution.
Preferably, in the step (2), the step of washing the filter residue means that the filter residue is washed with water until the pH of the washed wastewater is neutral, and then is dried.
Preferably, in the step (3), the addition amount of the asphalt is 10% -30%.
Further preferably, in the step (3), the addition amount of the asphalt is 10% -20%. The surface of the formed monomer structure is coated with a layer of uniform carbonaceous material in a ball milling mixing mode, and then the asphalt coated on the surface is partially decomposed through pyrolysis reaction, so that a layer of stable porous carbonaceous structure is formed on the surface of the catalytic material, and the stability of the spatial structure of the catalytic material and the cycle service life of the catalytic material can be enhanced.
Preferably, in the step (3), the ball milling time is 0.5-1h, and the ball milling revolution is 300-400 rpm.
Preferably, in step (3), the roasting conditions are: under inert atmosphere, the temperature is raised to 300-400 ℃ at the heating rate of 3-10 ℃/min, the temperature is kept for 2-3 hours, and then the temperature is raised to 500-550 ℃ at the heating rate of 3-10 ℃/min, and the temperature is kept for 1-2 hours.
Further preferably, in step (3), the conditions of the calcination are: under inert atmosphere, the temperature is raised to 300-350 ℃ at the heating rate of 3-5 ℃/min, the temperature is kept for 2-3 hours, and then the temperature is raised to 500-550 ℃ at the heating rate of 3-5 ℃/min, and the temperature is kept for 1-2 hours.
Preferably, in the step (3), the washing is performed by using a dilute acid solution with the concentration of 0.5% -1%, then washing with water, and drying after the pH value of the washed wastewater is neutral.
A heterogeneous catalytic material prepared by the preparation method as described above.
The use of a heterogeneous catalytic material as described above for the treatment of wastewater containing organic phosphorus.
The Fe in Fenton sludge mainly comprises ferric hydroxide (FeOOH) and ferric hydroxide (Fe (OH) 3 ) In the form of (2) is calcined at a certain temperature and then subjected to dehydrogenation reaction to form Fe 3 O 4 The magnetic separation performance is achieved, and different structures can be formed by doping other elements in the process and controlling reaction conditions, such as:
Mn(OH) 2 +Fe(OH) 3 →MnFe 2 O 4 +H 2 O
after roasting, a Mn (II)/Fe (III) heterogeneous structure system is formed, and electrons transfer and H catalysis are carried out on the Mn (II)/Fe (III) 2 O 2 Generating a large amount of OH and O 2 -free radicals to degrade organic phosphorus in the wastewater into free inorganic phosphorus; and then the MgO nano structure formed on the surface of the catalytic material can realize the super-enrichment adsorption effect on inorganic phosphorus and achieve the effect of removing phosphorus in wastewater.
The beneficial effects of the invention are as follows:
(1) According to the invention, firstly, metal elements in Fenton sludge are dissolved by acid washing, a certain amount of Mn and Mg-containing solution is added, and then, a chelating flocculant and a pH regulator are added, so that on one hand, the chelating flocculant and metal ions can be utilized to form a stable chelate, and the capacity of chelating and removing heavy metals is realized, and the flocculation sedimentation effect is realized; on the other hand, the chelating flocculant can be introduced as a carbon source, and can reduce high-valence metal ions (Fe is reduced in the subsequent pyrolysis reaction process 3+ 、Mn 4+ Reduction to Fe 2+ 、Mn 2 + ) The catalytic performance of the catalytic material is enhanced; furthermore, the pH regulator regulates the pH of the mixed solution to be specific, so that the stability of chelate formed by the chelating flocculant and metal ions is enhanced.
(2) The invention adopts pyrolysis technology to prepare magnetic MnFe 2 O 4 Catalytic material with crystal structure, on one hand, can be addedSpecific surface area, increased pollutant and inner MnFe of coating layer 2 O 4 The contact area of the structural monomer is utilized to generate mobile e-catalysis H between Fe (III)/Mn (II) 2 O 2 A large amount of OH is generated, organic matters in the wastewater are degraded, and the catalytic performance of the material is improved; on the other hand, a surface carbon coating technology is adopted, a layer of uniform carbonaceous material is coated on the surface of the formed monomer structure in a ball milling mixing mode, part of organic matters in the asphalt coated on the surface are decomposed through pyrolysis reaction to form a porous structure, and a chelating flocculant (dithiocarboxylated aminomethylpolyacrylamide) in the catalytic material coated inside is decomposed at a high temperature to reduce part of high-valence metal ions in the catalytic material and generate a large amount of gas, so that the specific surface area of the catalytic material is further improved. In addition, a layer of stable carbonaceous structure is formed on the surface of the catalytic material after pyrolysis, so that the stability of the spatial structure of the catalytic material can be enhanced and the cycle service life of the catalytic material can be prolonged.
(3) The heterogeneous catalytic material prepared by utilizing Fenton sludge has good magnetism, a magnetic separation technology can be adopted in the secondary recovery process, the separation efficiency and recovery efficiency are improved, the catalytic material can be used as a dephosphorization adsorption material to be applied to the wastewater treatment process containing organic phosphorus, the aim of treating waste with waste is fulfilled, and the development requirement of recycling economy is met.
Drawings
FIG. 1 is a schematic diagram of the preparation flow of a heterogeneous catalytic material according to example 1 of the present invention;
FIG. 2 is a flow chart of the overall synthesis of the heterogeneous catalytic material of example 1 of the present invention;
FIG. 3 is a diagram showing the monomer composite structure of the heterogeneous catalytic material of example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
a preparation method of a heterogeneous catalytic material, as shown in fig. 1 and 2, comprises the following steps:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 2% hydrochloric acid solution are mixed according to the volume ratio of 1:10, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 60 ℃, and stirring and reacting for 1.5 hours to obtain Fenton sludge acid washing suspension;
(3) To the obtained suspension, manganese ions were added: iron ions: the molar ratio of magnesium ions is 1:2:1, synchronously dropwise adding a magnesium chloride solution and a manganese chloride solution, and continuously stirring and reacting for 1h to obtain a mixed solution;
(4) Slowly dropwise adding a 2% DTAPAM (dithiocarboxylated amine methyl polyacrylamide) solution and 5% ammonia water into the mixed solution obtained in the step (3), keeping the reaction temperature at 55 ℃ until the pH of the mixed solution is stabilized at 9.8, continuously slowly stirring and reacting for 3 hours, and standing and ageing for 12 hours to obtain an ageing liquid;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 1:9, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 1h, and the revolution is 300 r/min);
(7) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 350 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 500 ℃, the temperature rising rate is 5 ℃/min, the constant temperature is maintained for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(8) The sample is firstly washed by 0.5% dilute hydrochloric acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the magnetic porous heterogeneous catalytic material.
The heterogeneous catalytic material is prepared by the preparation method, and the monomer composite structure diagram of the prepared heterogeneous catalytic material is shown in figure 3.
Example 2:
a method for preparing a heterogeneous catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 2% hydrochloric acid solution are mixed according to the volume ratio of 1:10, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 60 ℃, and stirring and reacting for 1.5 hours to obtain Fenton sludge acid washing suspension;
(3) To the obtained suspension, manganese ions were added: iron ions: the molar ratio of magnesium ions is 1:2:1, synchronously dropwise adding a magnesium chloride solution and a manganese chloride solution, and continuously stirring and reacting for 1h to obtain a mixed solution;
(4) Slowly dropwise adding a 2% DTAPAM (dithiocarboxylated amine methyl polyacrylamide) solution and 5% ammonia water into the mixed solution obtained in the step (3), keeping the reaction temperature at 60 ℃ until the pH value of the mixed solution is stabilized at 9.8, continuously slowly stirring and reacting for 3 hours, and standing and ageing for 12 hours to obtain an ageing liquid;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 1:9, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 1h, and the revolution is 300 r/min);
(7) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 300 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 550 ℃, the temperature rising rate is 5 ℃/min, the temperature is kept constant for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(8) The sample is firstly washed by 0.5% dilute hydrochloric acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the magnetic porous heterogeneous catalytic material.
A heterogeneous catalytic material is prepared by the preparation method.
Example 3:
a method for preparing a heterogeneous catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 2% hydrochloric acid solution are mixed according to the volume ratio of 1:10, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 60 ℃, and stirring and reacting for 1.5 hours to obtain Fenton sludge acid washing suspension;
(3) To the obtained suspension, manganese ions were added: iron ions: the molar ratio of magnesium ions is 1:1:1, synchronously dropwise adding a magnesium chloride solution and a manganese chloride solution, and continuously stirring and reacting for 1h to obtain a mixed solution;
(4) Slowly dropwise adding 2% of DTMPAM (dithiocarboxylated methylol polyacrylamide) solution and 7% of ammonia water into the mixed solution obtained in the step (3), keeping the reaction temperature at 60 ℃ until the pH of the mixed solution is stabilized at 10, continuously slowly stirring and reacting for 3 hours, and standing and ageing for 12 hours to obtain an ageing liquid;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 1.5:8.5, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 1h, and the revolution is 300 r/min);
(7) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 350 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 550 ℃, the temperature rising rate is 5 ℃/min, the temperature is kept constant for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(8) The sample is firstly washed by 0.5% dilute hydrochloric acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the magnetic porous heterogeneous catalytic material.
A heterogeneous catalytic material is prepared by the preparation method.
Example 4:
a method for preparing a heterogeneous catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 3% sulfuric acid solution are mixed according to the volume ratio of 1:9, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 70 ℃, and stirring and reacting for 1h to obtain Fenton sludge acid washing suspension;
(3) To the obtained suspension, manganese ions were added: iron ions: the molar ratio of magnesium ions is 1:1:1, synchronously dropwise adding a magnesium chloride solution and a manganese chloride solution, and continuously stirring and reacting for 1h to obtain a mixed solution;
(4) Slowly dropwise adding a 2% DTSPAM (dithiocarboxylated sulfomethyl polyacrylamide) solution and 10% ammonia water into the mixed solution obtained in the step (3), keeping the reaction temperature at 65 ℃ until the pH of the mixed solution is stabilized at 10, continuously slowly stirring and reacting for 3 hours, and standing and ageing for 12 hours to obtain an ageing liquid;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 2:8, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 0.5h, and the revolution is 400 r/min);
(7) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 400 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 550 ℃, the temperature rising rate is 5 ℃/min, the temperature is kept constant for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(8) The sample is firstly washed by 0.5% dilute hydrochloric acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the magnetic porous heterogeneous catalytic material.
A heterogeneous catalytic material is prepared by the preparation method.
Comparative example 1: (in comparison with example 1, the difference is that only magnesium-supported and pyrolysis reactions were carried out after pretreatment)
A method for preparing a catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Uniformly dispersing Fenton sludge powder in a magnesium chloride solution (according to the molar ratio of iron ions to magnesium ions being 2:1), slowly dripping 5% ammonia water, continuously and slowly stirring for reaction, controlling the pH value of a reaction system to be 9.8, controlling the reaction temperature to be 55 ℃, controlling the reaction time to be 3 hours, and after the reaction is finished, performing solid-liquid separation to dry filter residues to obtain a sample material;
(3) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 350 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 500 ℃, the temperature rising rate is 5 ℃/min, the constant temperature is maintained for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(4) The sample is firstly washed by 0.5% dilute acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the catalytic material.
Comparative example 2: (in comparison with example 1, the pretreatment was followed by manganese loading and surface coating only)
A method for preparing a catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 2% hydrochloric acid solution are mixed according to the volume ratio of 1:10, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 60 ℃, and stirring and reacting for 1.5 hours to obtain Fenton sludge acid washing suspension;
(3) The molar ratio of manganese ions to iron ions in the suspension is 1:2, slowly and synchronously dripping a manganese chloride solution, and continuously stirring and reacting for 1.5 hours to obtain a mixed solution;
(4) Slowly dripping ammonia water with the mass fraction of 5% into the mixed solution, keeping the reaction temperature at 55 ℃ until the pH value of the mixed solution is stabilized at 9.8, continuously slowly stirring and reacting for 3 hours, and standing and aging for 12 hours to obtain an aged solution;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 1:9, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 1h, and the revolution is 300 r/min), so as to obtain the catalytic material.
Comparative example 3: (in comparison with example 1, the difference is that only manganese-supported, surface-coating and pyrolysis reactions were carried out after pretreatment)
A method for preparing a catalytic material, comprising the steps of:
(1) Drying, crushing and sieving Fenton sludge to obtain Fenton sludge powder;
(2) Fenton sludge powder and 2% hydrochloric acid solution are mixed according to the volume ratio of 1:10, mixing, carrying out acid washing treatment in a constant-temperature water bath kettle at 60 ℃, and stirring and reacting for 1.5 hours to obtain Fenton sludge acid washing suspension;
(3) The molar ratio of manganese ions to iron ions in the suspension is 1:2, slowly and synchronously dripping a manganese chloride solution, and continuously stirring and reacting for 1h to obtain a mixed solution;
(4) Slowly dripping ammonia water with the mass fraction of 5% into the mixed solution, keeping the reaction temperature at 55 ℃ until the pH value of the mixed solution is stabilized at 9.8, continuously slowly stirring and reacting for 3 hours, and standing and aging for 12 hours to obtain an aged solution;
(5) After the aging liquid is subjected to solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;
(6) The mass ratio of the catalytic material precursor to asphalt is 1:9, mixing, and uniformly coating asphalt on the surface of the catalytic material precursor by adopting a ball milling mode (the ball milling time is 1h, and the revolution is 300 r/min);
(7) Placing the sample material into an atmosphere furnace for pyrolysis, wherein the roasting conditions are as follows: heating rate 5 ℃/min, constant temperature 350 ℃, constant temperature 2h and N 2 An atmosphere; then the temperature is increased to 500 ℃, the temperature rising rate is 5 ℃/min, the constant temperature is maintained for 1h, and N 2 After the pyrolysis reaction is finished, cooling to room temperature, and taking out a sample;
(8) The sample is firstly washed by 0.5% dilute hydrochloric acid solution, then washed by water until the pH value is neutral, and then dried and ground to obtain the catalytic material.
Test example:
1. the specific surface areas of the heterogeneous catalytic materials of examples 1 to 4 and the catalytic materials of comparative examples 1 to 3 were measured, respectively, and the measurement results are shown in Table 1.
2. Phosphorus removal test: respectively taking 0.03g of the heterogeneous catalytic materials of examples 1-4 and 0.03g of the catalytic materials of comparative examples 1-3, respectively adding the heterogeneous catalytic materials into 100mL of simulated wastewater containing organic phosphorus with the concentration of 100mg/L and the pH value of 3.5, adding 1mL of 30% hydrogen peroxide, stirring and reacting for 3 hours, filtering the catalytic materials after the reaction is finished, measuring the residual content of phosphorus in the water body, calculating the phosphorus removal rate, and testing the result shown in Table 1.
3. The phosphorus removal test was repeated 5 times, and each test was completed by washing the heterogeneous catalytic materials of examples 1 to 4 and the catalytic materials of comparative examples 1 to 3 with a 1:1 mixture of 0.5mol/L HCl solution and 0.5mol/L LNaCl solution, filtering and washing the washed catalytic materials, and vacuum drying for recycling. The recycling effect of the catalytic material was measured each time, the phosphorus removal rate at the 5 th time was recorded, and the test results are shown in table 1.
Table 1: experimental results
As can be seen from Table 1, the specific surface area of the heterogeneous catalytic material prepared by the preparation method of the invention reaches 308.79m 2 The first maximum equilibrium removal amount reaches more than 268.27mg/g, the first phosphorus removal rate reaches more than 80.48%, and the 5 th phosphorus removal rate reaches more than 63.47% during recycling.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a heterogeneous catalytic material is characterized by comprising the following steps: the method comprises the following steps:
(1) Carrying out acid washing treatment on Fenton sludge to obtain Fenton sludge acid washing suspension, and then adding a magnesium salt solution and a manganese salt solution to obtain a mixed solution;
(2) Adding a chelating flocculant and a pH regulator into the mixed solution prepared in the step (1), aging after reaction to obtain an aged solution, carrying out solid-liquid separation on the aged solution, cleaning and drying the obtained filter residues to obtain a catalytic material precursor;
(3) Mixing the catalytic material precursor prepared in the step (2) with asphalt, ball-milling, roasting, cooling, cleaning and drying to obtain the heterogeneous catalytic material.
2. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1: (0.8-3): (0.8-1.2).
3. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (2), the chelating flocculant is at least one of dithiocarboxylated methylol polyacrylamide, dithiocarboxylated sulfomethyl polyacrylamide and dithiocarboxylated aminomethyl polyacrylamide.
4. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (2), the pH regulator is ammonia water with the mass fraction of 5% -10%.
5. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (2), the temperature of the reaction is 50-70 ℃.
6. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (2), the chelating flocculant and the pH regulator are added dropwise, and after the pH in the mixed solution is stabilized between 9.8 and 10.5, the mixed solution is continuously stirred for 2 to 4 hours, and then is kept stand and aged for 10 to 15 hours, so that the aged solution is obtained.
7. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (3), the addition amount of the asphalt is 10% -30%.
8. The method for preparing a heterogeneous catalytic material according to claim 1, wherein: in the step (3), the roasting conditions are as follows: under inert atmosphere, the temperature is raised to 300-400 ℃ at the heating rate of 3-10 ℃/min, the temperature is kept for 2-3 hours, and then the temperature is raised to 500-550 ℃ at the heating rate of 3-10 ℃/min, and the temperature is kept for 1-2 hours.
9. A heterogeneous catalytic material, characterized by: the heterogeneous catalytic material is prepared by the preparation method of any one of claims 1-8.
10. Use of the heterogeneous catalytic material of claim 9 for treating wastewater containing organic phosphorus.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2023082854 | 2023-03-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116829262A true CN116829262A (en) | 2023-09-29 |
Family
ID=88114970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202380009012.8A Pending CN116829262A (en) | 2023-03-21 | 2023-03-21 | Heterogeneous catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116829262A (en) |
-
2023
- 2023-03-21 CN CN202380009012.8A patent/CN116829262A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019051923A1 (en) | Iron-containing sludge pyrolysis residue-based sludge complex conditioning agent, preparation therefor and use thereof | |
| CN111389363B (en) | Magnetic biochar adsorbing material based on sulfate-reduced sludge and preparation method and application thereof | |
| CN111921536B (en) | Novel catalytic adsorption material prepared based on natural minerals and biomass | |
| CN106540672A (en) | A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation | |
| CN110694583A (en) | Preparation method and application of magnetic recyclable lanthanum oxycarbonate phosphorus removal adsorbent | |
| CN111389435A (en) | Iron-carbon micro-electrolysis-Fenton-like catalytic system and application | |
| CN113877581A (en) | Copper ferrite spinel material and preparation method and application thereof | |
| CN107552052B (en) | Treatment method of refractory organic wastewater | |
| CN107840415A (en) | A kind of method that iron-carbon micro-electrolysis filler is prepared using pickling iron cement | |
| CN111847820A (en) | Sludge dewatering method based on hydrothermal method | |
| CN109622055B (en) | Iron-manganese bimetallic catalyst based on iron carbide-based MOFS (metal oxide semiconductor) and preparation method thereof | |
| CN112374583B (en) | Preparation and application of functionalized sludge-based carbon three-dimensional particle electrode | |
| CN114345344A (en) | Persulfate catalyst and preparation method and application thereof | |
| CN111068615B (en) | Multi-element composite adsorption material for removing vanadium and preparation method and application thereof | |
| CN110092438B (en) | Method for treating organic wastewater by using electrolytic manganese residues as photocatalyst | |
| CN116655091A (en) | Method for removing organic pollutants in water body by utilizing Fe-N-C activated sulfite | |
| CN116829262A (en) | Heterogeneous catalytic material and preparation method and application thereof | |
| CN103691448B (en) | The preparation method of magnetic sludge base ozone catalyst and application | |
| Yuan et al. | Preparation of chitosan mesoporous membrane/halloysite composite for efficiently selective adsorption of Al (III) from rare earth ions solution through constructing pore structure on substrate | |
| CN114452999B (en) | Fe for purifying antibiotic wastewater 2 Preparation method of P/NPGC catalyst | |
| CN114100573B (en) | Preparation method of MOFs-derived porous carbon-coated iron oxide composite material | |
| CN115845870A (en) | Three-way catalyst and preparation method and application thereof | |
| CN107673436A (en) | The method for preparing by iron-carbon micro-electrolysis offal treatment sewage and subsequently catalysis nitro reducing catalyst | |
| CN114054027A (en) | Graphite material modified red mud Fenton catalyst with magnetic separation performance and preparation method and application thereof | |
| CN109647410B (en) | Preparation method of supported expanded graphite catalyst for treating EDTA-Cu wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |