CN113559840A - Auto-oxidation catalyst, preparation method and method for removing organic matters in high-salinity wastewater - Google Patents
Auto-oxidation catalyst, preparation method and method for removing organic matters in high-salinity wastewater Download PDFInfo
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Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/72—Copper
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses an autoxidation catalyst, a preparation method and a method for removing organic matters in high-salinity wastewater, wherein the autoxidation catalyst comprises the following components: the core-shell structure comprises a first core-shell layer, a second core-shell layer and a coating layer, wherein the first core-shell layer comprises a graphitized carbon nano layer taking iron phosphide as a core; the second core shell layer comprises a graphitized carbon nano layer taking copper as an inner core; the first core shell layer and the second core shell layer are disposed in the embedding layer.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to an autoxidation catalyst, a preparation method and a method for removing organic matters in high-salinity wastewater.
Background
When the mass fraction of organics and Total Dissolved Solids (TDS) in the wastewater is greater than 3.5%, such wastewater is referred to as high salinity wastewater. The high-salt wastewater contains a large amount of organic pollutants and a large amount of soluble inorganic salts such as Cl-、Na+、SO4 2-、Ca2+And the like. Therefore, when such waste water is treated, there is a limit to biochemical treatment.
The high-salt wastewater is mainly derived from a large amount of inorganic salts used in the chemical agent (such as insecticide) manufacture in chemical production; sodium hydroxide, hypochlorous acid and other alkaline substances added in the refining and bleaching processes of the dye generate a large amount of inorganic salt; and the seawater is applied to inorganic salt and the like generated in the industries of thermoelectricity, nuclear power, petrifaction, metallurgy, steel and the like.
When the high-salinity wastewater is discharged into the environment without treatment and permeates and flows into a soil system, the high salinity of the high-salinity wastewater can dehydrate and die organisms and plants in the soil to cause the disruption of the soil ecosystem, and in addition, the high-salinity wastewater directly discharged can bring greater pressure to the water environment. Therefore, the research on the desalination technology of high-salinity wastewater is urgent, and the search for an effective desalination treatment technology of high-salinity wastewater has become one of the hot spots of the current wastewater treatment.
The conventional methods for treating high-salinity wastewater include ion exchange method, electrodialysis method, reverse osmosis method, high-temperature incineration method, distillation method, osmosis method and the like. The ion exchange technology is mature, and can be used for desalting treatment, but the ion exchange period is long, the operation is complex, and the method is generally suitable for treating low-salinity wastewater. The electrodialysis method is not very thorough in desalting and only partially removes the salt. Although the reverse osmosis method is widely used in treating salt-containing wastewater, the conventional reverse osmosis treatment method cannot effectively concentrate such high-salt wastewater, and has a problem of treating the concentrated wastewater generated by the reverse osmosis; although the high-temperature incineration method can directly oxidize organic matters, the equipment investment and maintenance cost is high, and the corrosivity of salt to equipment in the combustion process is not low. The membrane technology is high in equipment cost, easy to block and easy to pollute. In short, the methods have the problems of large investment, complex process, high energy consumption, high treatment cost and the like.
At present, the prior art mainly adopts advanced oxidation technologies including ozone oxidation, Fenton or electric Fenton, photocatalysis and the like to remove organic pollutants in wastewater, but the ozone oxidation method has higher equipment and operation cost, UV photolysis is greatly influenced by water quality, a Fenton or electric-Fenton catalytic oxidation process requires specific reaction conditions, more iron-containing sludge is easily generated, and the method is economical to use only when the pH value of saline raw water is low. In addition, the advanced oxidation technologies need to additionally add oxidants such as hydrogen peroxide, the generated strong oxidant-hydroxyl free radical is used for degrading organic matters, the hydroxyl free radical is a nonselective oxidant, the oxidizing capability of the hydroxyl free radical is extremely strong, and the hydroxyl free radical can rapidly perform a chain reaction with most organic pollutants to oxidize harmful substances into CO2、H2O or a mineral salt. But the hydroxyl free radical can also be replaced by Cl in high-salinity wastewater-、SO4 2-、PO4 3-、CO3 2-And (3) quenching by plasma, such as reacting with chloride ions to generate chlorine free radicals and chlorine atoms, so that the Fenton oxidation completely fails to remove organic matters in the high-salinity wastewater.
Therefore, the improvement of the selective degradation of the autoxidation catalyst to organic pollutants is the key for the successful pretreatment of the high-salinity wastewater, thereby solving the problems of low efficiency, complex process, large amount of generated sludge and difficult standard reaching of the wastewater in the high-salinity wastewater treatment by the advanced oxidation technology.
Disclosure of Invention
In view of the above, the present invention provides an autoxidation catalyst, a preparation method thereof, and a method for removing organic matters in high-salinity wastewater, so as to at least partially solve the above technical problems.
To achieve the above technical object, as one aspect of the present invention, there is provided an autoxidation catalyst comprising: the core-shell structure comprises a first core-shell layer, a second core-shell layer and a coating layer, wherein the first core-shell layer comprises a graphitized carbon nano layer taking iron phosphide as a core; the second core shell layer comprises a graphitized carbon nano layer taking copper as an inner core; the first core shell layer and the second core shell layer are disposed in the embedding layer.
The embodiment of the invention also provides a method for preparing the autoxidation catalyst, which comprises the following steps: mixing a carbon source and a phosphorus source, and drying at a first preset temperature to obtain a first mixture; uniformly mixing the first mixture with an iron source, a copper source and an adhesive to obtain a second mixture; and forming and drying the second mixture, and carbonizing the second mixture in a nitrogen atmosphere to obtain the autoxidation catalyst containing the first core-shell layer, the second core-shell layer and the embedded layer.
According to an embodiment of the present invention, the carbon source comprises at least one of: agricultural and forestry wastes, activated sludge, animal wastes and kitchen wastes; the phosphorus source comprises at least one of: phosphoric acid, phosphoric acid-containing waste liquid; the iron source comprises at least one of the following: iron mud, iron ore, ferric chloride, ferrous chloride and ferrous sulfate; the copper source comprises at least one of: basic copper carbonate, copper sulfate and copper chloride, wherein the binder is selected from clay minerals.
According to the embodiment of the invention, the carbon source and the phosphorus source are mixed and dried at a first preset temperature to obtain a first mixture, wherein the first mixture is obtained by mixing 0.3-10 kg of the carbon source in each liter of the phosphorus source and drying at 50-250 ℃.
According to the embodiment of the invention, the mass ratio of the first mixture to the iron source is 5: 1-1: 5; the mass ratio of the iron source to the copper source is 5: 1-1: 2, and the mass ratio of the adhesive to the main raw material is 1: 10-1: 5.
According to an embodiment of the present invention, the above-mentioned second mixture is molded, dried, and then carbonized in a nitrogen atmosphere to obtain the autoxidation catalyst, which comprises: and (3) forming and drying the second mixture, and then carbonizing the second mixture for 0.5-5 hours at 600-1000 ℃ in a nitrogen atmosphere to obtain the auto-oxidation catalyst.
The embodiment of the invention also comprises a method for removing the organic matters in the high-salinity wastewater by adopting the auto-oxidation catalyst.
According to the embodiment of the invention, the method comprises the following steps: filling the autoxidation catalyst in a catalyst reactor; adding high-salinity wastewater into the catalyst reactor, and degrading organic matters in the high-salinity wastewater for a first preset reaction time; and sequentially carrying out coagulation treatment and flocculation treatment on the degraded high-salinity wastewater to remove the degraded organic matters in the high-salinity wastewater.
According to an embodiment of the present invention, the first preset reaction time period includes 30-120 min.
According to the embodiment of the invention, the method further comprises the following steps: and filling an autoxidation catalyst filler in the catalyst reactor, wherein the filling density of the autoxidation catalyst filler is 60-80%.
The autoxidation catalyst material prepared by the invention belongs to an iron-carbon internal electrolysis material, and active ingredients of iron phosphide and graphitized carbon form a core-shell structure and are embedded in a flaky graphitized carbon layer, so that zero-valent iron is effectively prevented from being corroded by oxygen in the storage process; the zero-valent copper nano-additive can promote the corrosion of iron phosphide and release more electrons, so that when Fenton oxidation is carried out, after the electrons released by the iron phosphide are captured by dissolved oxygen in water, various active oxygen substances are generated through chain reaction, thereby promoting the oxidative degradation of organic matters; the autoxidation catalyst material has high activity and structural stability, relieves the loss of zero-valent iron, hardly loses phosphorus element in the material, reduces the generation of red mud in the industrial wastewater treatment process, does not introduce phosphorus pollution in wastewater, improves the adsorption and capture capacity of the material to organic matters by using an activated carbon carrier in the material, and is beneficial to selectively removing pollutants by using active oxygen substances generated on the surface of the material, thereby realizing the selective degradation of the autoxidation catalyst to the organic pollutants.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a scanning electron microscope image of an autoxidation catalyst material obtained by using chicken manure as a carbon source.
FIG. 2 is a scanning electron microscope image of the auto-oxidation catalyst material obtained by using coffee grounds as a carbon source according to the present invention.
FIG. 3 is an XRD spectrum of the auto-oxidation catalyst material obtained by using chicken manure as a carbon source and coffee grounds as a carbon source.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available.
When the catalyst in the prior art is used for performing Fenton oxidation reaction to treat wastewater, oxidants such as hydrogen peroxide are additionally added, and most harmful substances can be oxidized into CO due to over strong oxidizing property of the hydrogen peroxide2、H2O or mineral salts, and simultaneously, the anions in the high-salinity wastewater are quenched, so that the removal of the organic matters in the high-salinity wastewater by Fenton oxidation is completely ineffective. Therefore, the improvement of the selective degradation of the autoxidation catalyst to organic pollutants is the key for the successful pretreatment of the high-salinity wastewater, thereby solving the problems of low efficiency, complex process, large amount of generated sludge and difficult standard reaching of the wastewater in the high-salinity wastewater treatment by the advanced oxidation technology.
Accordingly, the present invention provides an autoxidation catalyst comprising: the core-shell structure comprises a first core-shell layer, a second core-shell layer and a coating layer, wherein the first core-shell layer comprises a graphitized carbon nano layer taking iron phosphide as a core; the second core shell layer comprises a graphitized carbon nano layer taking copper as an inner core; the first core shell layer and the second core shell layer are disposed in the embedding layer.
In the embodiment of the invention, the core-shell structure formed by the active ingredients of the iron phosphide and the graphitized carbon is embedded in the flaky graphitized carbon, so that zero-valent iron can be prevented from being corroded by oxygen in the storage process, the corrosion of the iron phosphide can be promoted by the core-shell structure formed by the copper and the graphitized carbon, more electrons are released, and thus, when Fenton oxidation is carried out, after electrons released by the iron phosphide are captured by dissolved oxygen in water, various active oxygen substances are generated through chain reaction, and the oxidative degradation of organic matters is promoted.
The embodiment of the invention also provides a method for preparing the autoxidation catalyst, which comprises the following steps: mixing a carbon source and a phosphorus source, and drying at a first preset temperature to obtain a first mixture; uniformly mixing the first mixture with an iron source, a copper source and an adhesive to obtain a second mixture; and forming and drying the second mixture, and carbonizing the second mixture in a nitrogen atmosphere to obtain the autoxidation catalyst containing the first core-shell layer, the second core-shell layer and the embedded layer.
In the embodiment of the invention, a first mixture formed by a carbon source and a phosphorus source is mixed with an iron source, a copper source and an adhesive, the mixture is dried, molded and carbonized at high temperature to obtain an autoxidation catalyst containing a first nuclear shell layer, a second nuclear shell layer and an embedding layer, the autoxidation catalyst obtains active ingredient nano iron phosphide, carrier and graphitized carbon of an organic matter adsorption center and auxiliary agent nano copper particles in the high-temperature carbonization process, the nano iron phosphide is from the reduction of the organic carbon to the iron source at high temperature, has stronger stability and is not easily oxidized by oxygen in the air in the storage process; the assistant nano copper particles are from reduction of copper salt by carbon element, and the assistant nano copper can promote corrosion of iron phosphide and release more electrons; the graphitized carbon in the carrier and organic adsorption center comes from the carbonization of carbon source.
According to an embodiment of the present invention, the carbon source comprises at least one of: agricultural and forestry wastes, activated sludge, animal wastes and kitchen wastes; the phosphorus source comprises at least one of: phosphoric acid, phosphoric acid-containing waste liquid; the iron source comprises at least one of the following: iron mud, iron ore, ferric chloride, ferrous chloride and ferrous sulfate; the copper source comprises at least one of: basic copper carbonate, copper sulfate and copper chloride, wherein the binder is selected from clay minerals.
In the embodiment of the invention, the phosphorus source, the carbon source and the iron source are all selected from industrial or agricultural and forestry wastes, the raw materials are easy to obtain, the cost of the materials is reduced, and a zero-emission treatment method for the industrial and agricultural and forestry wastes is provided, so that the method has a very good application prospect.
According to the embodiment of the invention, the carbon source and the phosphorus source are mixed and dried at a first preset temperature to obtain a first mixture, wherein the first mixture is obtained by mixing 0.3-10 kg of the carbon source in each liter of the phosphorus source and drying at 50-250 ℃.
In the embodiment of the present invention, each liter of the phosphorus source may be mixed with any one of the following carbon sources: 0.3kg, 3kg, 8kg, 10 kg. The drying temperature may be, for example, any one of the following temperatures: 50 ℃, 100 ℃, 150 ℃ and 250 ℃.
According to the embodiment of the invention, the mass ratio of the first mixture to the iron source is 5: 1-1: 5; the mass ratio of the iron source to the copper source is 5: 1-1: 2, and the mass ratio of the adhesive to the main raw material is 1: 10-1: 5.
In the embodiment of the invention, the raw materials are prepared according to the mass ratio of carbon, phosphorus, iron and copper elements, wherein the mass ratio of carbon is 3-35%, the mass ratio of phosphorus is 5-20%, the mass ratio of iron is 20-50% and the mass ratio of copper is 5-20%, and a binder is further added into the mixture of the raw materials, and accounts for 0-20% of the total weight of the main raw materials.
In an embodiment of the present invention, a mass ratio of the first mixture to the iron source is 5: 1 to 1: 5, and may be any one of the following mass ratios: 5: 1, 4: 2, 3: 3, 1: 5; the mass ratio of the iron source to the copper source is 5: 1 to 1: 2, and may be any one of the following mass ratios: 5: 1, 4: 1, 2: 3 and 1: 2, wherein the mass ratio of the adhesive to the main raw materials is 1: 10-1: 5.
According to an embodiment of the present invention, the above-mentioned second mixture is molded, dried, and then carbonized in a nitrogen atmosphere to obtain the autoxidation catalyst, which comprises: and (3) forming and drying the second mixture, and then carbonizing the second mixture for 0.5-5 hours at 600-1000 ℃ in a nitrogen atmosphere to obtain the auto-oxidation catalyst.
In the embodiment of the invention, in a nitrogen atmosphere, at 600-1000 ℃, for example: carbonizing at 600 deg.C, 700 deg.C, 800 deg.C and 1000 deg.C for 0.5h, 2h, 4h and 5h to obtain the autoxidation catalyst.
In the embodiment of the invention, the autoxidation catalyst material belongs to an iron-carbon internal electrolysis material, and has the advantages of good stability, difficult hardening and long service cycle. The active center of the currently and generally used iron-carbon internal electrolysis material is zero-valent iron, which is easily oxidized by oxygen in the air and easily lost in the wastewater treatment process, thereby losing activity. The active component of the auto-oxidation catalytic material is iron phosphide, so that the auto-oxidation catalytic material has stronger stability and is not easily oxidized by oxygen in the air in the storage process; the special structure of the iron phosphide enables zero-valent iron to be difficult to lose, so that the activity of the iron phosphide can be maintained for a long time, the generation of iron mud is reduced, phosphorus element in the material is hardly lost, the generation of red mud in the industrial wastewater treatment process is reduced, phosphorus pollution cannot be introduced into wastewater, the adsorption and capture capacity of the material on organic matters is improved by the activated carbon carrier in the material, and the selective removal of active oxygen substances generated on the surface of the material on pollutants is facilitated.
According to the embodiment of the invention, the method for removing the organic matters in the high-salinity wastewater by using the auto-oxidation catalyst is included.
In the embodiment of the invention, the autoxidation catalyst material has strong adsorption capacity on organic matters and unique dissolved oxygen activation capacity, and can generate more active oxygen substances in wastewater, thereby promoting the selective and efficient removal of the organic matters in the high-salinity wastewater.
According to the embodiment of the invention, the method comprises the following steps: laying the autoxidation catalyst in a catalyst reactor; adding high-salinity wastewater into the catalyst reactor, and degrading organic matters in the high-salinity wastewater for a first preset reaction time; and sequentially carrying out coagulation treatment and flocculation treatment on the degraded high-salinity wastewater to remove the degraded organic matters in the high-salinity wastewater.
In the embodiment of the invention, the concentration of active oxygen generated by the autoxidation catalyst material is high, and no additional H2O is needed2The pH of the wastewater does not need to be adjusted, and the method is suitable for removing organic matters in high-salinity wastewater with any pH; after the reaction, the pH value of the solution is raised to be alkalescent or alkaline, so that the step of adjusting the pH value of the effluent is omitted, and the flocculation treatment can be directly carried out,the method for removing the organic matters in the high-salinity wastewater by using the autoxidation catalyst material omits acid, alkali and H2O2The cost is saved.
According to an embodiment of the present invention, the first preset reaction time period includes 30-120 min.
In an embodiment of the present invention, the first preset reaction time includes 30 to 120min, for example: 30min, 60min, 90min and 120 min.
According to the embodiment of the invention, the method further comprises the following steps: and filling an autoxidation catalyst filler in the catalyst reactor, wherein the filling density of the autoxidation catalyst filler is 60-80%.
In an embodiment of the present invention, the packing density of the auto-oxidation catalyst filler includes 60 to 80%, for example: 60%, 70%, 75% and 80%.
The present invention will be described in detail with reference to specific examples.
The preparation method of the auto-oxidation catalyst material comprises the following steps:
example 1
Airing chicken manure as a carbon source, and taking waste liquid containing phosphoric acid as a phosphorus source; mixing a carbon source of chicken manure with a waste liquid containing phosphoric acid, heating and drying the carbon source in 8kg of carbon source in each liter of phosphorus source waste liquid at 150 ℃ to obtain a first mixture; mixing the first mixture and an iron source according to a mass ratio of 1: 1, mixing the iron source and a copper source according to a mass ratio of 2: 3, mixing a binder and the main raw materials according to a mass ratio of 1: 6, mechanically stirring or grinding uniformly by a machine to obtain a second mixture, forming and drying the second mixture to prepare formed particles, putting the formed particles into a high-temperature atmosphere furnace, and carbonizing at 800 ℃ for 4 hours in a nitrogen atmosphere to obtain the auto-oxidation catalyst.
Example 2
Crushing coffee grounds to be below 400 meshes as a carbon source, and taking waste liquid containing phosphoric acid as a phosphorus source; mixing a coffee grounds carbon source with phosphoric acid-containing waste liquid, mixing 8kg of coffee grounds carbon source in each liter of phosphoric acid waste liquid, heating at 150 ℃, and drying to obtain a first mixture; mixing the first mixture and an iron source according to a mass ratio of 1: 1, mixing the iron source and a copper source according to a mass ratio of 2: 3, mixing a binder and the main raw materials according to a mass ratio of 1: 6, mechanically stirring or grinding uniformly by a machine to obtain a second mixture, forming and drying the second mixture to prepare formed particles, putting the formed particles into a high-temperature atmosphere furnace, and carbonizing at 800 ℃ for 4 hours in a nitrogen atmosphere to obtain the auto-oxidation catalyst.
Scanning electron microscope and XRD spectrogram characterization of two autoxidation catalyst materials prepared in example 1 and example 2
Scanning Electron Microscope (SEM) characterization of the structures of the two autoxidation catalyst materials was as follows:
and analyzing the particle size and the morphology structure of the auto-oxidation catalyst-like material by using a Japanese Hitachi S-8020 field emission scanning electron microscope.
Fig. 1 and 2 are scanning electron micrographs of autoxidation catalyst materials obtained by using chicken manure as a carbon source and coffee grounds as a carbon source, respectively. As can be seen from fig. 1 and 2, the carbon-based material is in the form of nano-flakes, and iron phosphide and zero-valent copper are dispersed between the carbon flakes.
EXD detection and analysis are carried out on the autoxidation catalyst material obtained by taking the chicken manure as a carbon source and the coffee grounds as a carbon source, and the results are shown in the table. Table 1 shows the elemental composition of the autoxidation catalyst material obtained from different carbon sources, and the contents of each element in the two materials are shown in table 1.
TABLE 1 elemental composition of autoxidation catalyst materials derived from different carbon sources
As can be seen from Table 1, the two materials are mainly composed of C, O, P, Fe, Cu and Si, and the contents of the elements are close; the content of carbon element is low, and the content of iron phosphide and zero-valent copper is far higher than that of carbon element; the material also contains K, Ca, Al and other macroelements.
FIG. 3 is an X-ray diffraction (XRD) pattern of an autoxidation catalyst material of two different carbon sources obtained by filtering CuKalpha radiation using nickel on a b/max-RBDiffractometer (Rigaku, Japan) at a scan rate of 1 DEG/min ranging from 5 DEG to 90 DEG, as shown in FIG. 3, and as analyzed in conjunction with FIG. 3, the autoxidation catalyst material is composed mainly of SiO2、FeP/Fe2P and Cu0And (4) forming.
Example 3
The autoxidation catalyst material prepared in the example 1 is used for treating organic matters in high-salinity wastewater of pharmaceutical wastewater;
cl in the wastewater-The content is about 3000mg/L, the COD concentration is about 200ppm, the water sample is brown, the water sample contains various chloropyridine acids high-toxicity organic pollutants, and the organic matters in the wastewater are removed by using the auto-oxidation zero-valent iron material (expressed by the TOC removal rate).
The method comprises the following specific steps:
the method comprises the steps of using a reaction column with the diameter of 12mm multiplied by 300mm, filling an autoxidation catalyst material with the thickness of 200mm, allowing the contact reaction time to be 60min, enabling the pH value of raw water to be 7.14, pumping wastewater from the bottom of a reactor by using a micro peristaltic pump, enabling effluent to enter a water collecting tank, changing the pH value to 8.0-8.5, not needing to adjust the pH value additionally, standing for 30min, detecting the removal condition of organic matters by using an organic carbon analyzer, and testing the loss condition in the operation process by using ICP-MS. The results show that the removal rate of TOC is always maintained at 45-55%, and phosphate radical is not detected, and the loss rate of iron and copper is less than 1% of the material.
Example 4
For the catalyst prepared in example 1-2, 5 different industries of high salinity wastewater (Cl) were selected-Content is more than or equal to 3000mg/L) is tested on the performance of the autoxidation catalyst material, the COD content of the waste water is 100-200ppm, the initial pH of the waste water is 6.08-8.01, and the testing steps are the same as the example 3.
The results prove that the material can remove organic matters in high-salt wastewater to the highest efficiency within 60-90min without adjusting the pH and adding hydrogen peroxide, the TOC removal rate in 5 types of wastewater is 40-73%, a water sample is clear and colorless after reaction, the pH is increased to 6.53-9.03, and the wastewater can enter a flocculation tank for flocculation treatment or directly undergo a next treatment process without adjusting the pH.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An autoxidation catalyst comprising: a first core shell layer, a second core shell layer and an embedding layer,
the first nuclear shell layer comprises a graphitized carbon nano layer taking iron phosphide as an inner core;
the second core shell layer comprises a graphitized carbon nano layer taking copper as an inner core;
the first and second core-shell layers are disposed in the encapsulation layer.
2. A method of preparing the autoxidation catalyst of claim 1 comprising:
mixing a carbon source and a phosphorus source, and drying at a first preset temperature to obtain a first mixture;
uniformly mixing the first mixture with an iron source, a copper source and an adhesive to obtain a second mixture;
and forming and drying the second mixture, and carbonizing in a nitrogen atmosphere to obtain the autoxidation catalyst containing the first core-shell layer, the second core-shell layer and the embedded layer.
3. The method of claim 2, wherein,
the carbon source comprises at least one of: agricultural and forestry wastes, activated sludge, animal wastes and kitchen wastes;
the phosphorus source comprises at least one of: phosphoric acid, phosphoric acid-containing waste liquid;
the iron source comprises at least one of: iron mud, iron ore, ferric chloride, ferrous chloride and ferrous sulfate;
the copper source comprises at least one of: basic copper carbonate, copper sulfate and copper chloride.
4. The method of claim 2, wherein mixing the carbon source with the phosphorus source and drying at a first predetermined temperature to obtain a first mixture comprises mixing 0.3-10 kg of the carbon source per liter of the phosphorus source and drying at 50-250 ℃ to obtain the first mixture.
5. The method of claim 2, wherein the mass ratio of the first mixture to the iron source comprises 5: 1 to 1: 5; the mass ratio of the iron source to the copper source is 5: 1-1: 2.
6. The method of claim 2, wherein the second mixture is shaped, dried, and then carbonized in a nitrogen atmosphere to obtain the auto-oxidation catalyst, comprising: and (3) forming and drying the second mixture, and then carbonizing the second mixture for 0.5-5 hours at 600-1000 ℃ in a nitrogen atmosphere to obtain the auto-oxidation catalyst.
7. A method for removing organic matters in high-salinity wastewater, which comprises the step of removing the organic matters in the high-salinity wastewater by using the auto-oxidation catalyst as claimed in claim 1.
8. The method of claim 7, comprising:
packing the autoxidation catalyst in a catalyst reactor;
adding high-salinity wastewater into the catalyst reactor, and degrading organic matters in the high-salinity wastewater for a first preset reaction time;
and sequentially carrying out coagulation treatment and flocculation treatment on the degraded high-salinity wastewater to remove the degraded organic matters in the high-salinity wastewater.
9. The method of claim 7, wherein the first preset reaction time period comprises 30-120 min.
10. The method of claim 7, further comprising: and filling an autoxidation catalyst filler in the catalyst reactor, wherein the filling density of the autoxidation catalyst filler is 60-80%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351445A (en) * | 2023-02-28 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160024374A1 (en) * | 2014-07-23 | 2016-01-28 | Baker Hughes Incorporated | Ferrofluids absorbed on graphene/graphene oxide for eor |
| WO2018175594A1 (en) * | 2017-03-21 | 2018-09-27 | William Marsh Rice University | Thin films of transition metal phosphides coated on a semiconductor core from organometallic precursors for oxygen evolution and hydrogen evolution catalysis |
| CN109179594A (en) * | 2018-10-17 | 2019-01-11 | 中国科学院生态环境研究中心 | The preparation and application of the efficient Fenton catalyst of core-shell type iron-carbon micro-electrolytic material |
| CN109962245A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | Transition metal phosphide porous carbon nanosheet composite material and its preparation and application |
| CN110252305A (en) * | 2019-03-05 | 2019-09-20 | 中国科学院生态环境研究中心 | Keep the preparation and application of the iron-carbon micro-electrolytic material of the long-acting catalytic activity of Fenton system |
| CN110560168A (en) * | 2019-09-30 | 2019-12-13 | 天津工业大学 | Core-shell hierarchical iron/copper bimetallic Fenton catalyst and preparation method and application thereof |
-
2021
- 2021-08-12 CN CN202110927419.1A patent/CN113559840B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160024374A1 (en) * | 2014-07-23 | 2016-01-28 | Baker Hughes Incorporated | Ferrofluids absorbed on graphene/graphene oxide for eor |
| WO2018175594A1 (en) * | 2017-03-21 | 2018-09-27 | William Marsh Rice University | Thin films of transition metal phosphides coated on a semiconductor core from organometallic precursors for oxygen evolution and hydrogen evolution catalysis |
| CN109962245A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | Transition metal phosphide porous carbon nanosheet composite material and its preparation and application |
| CN109179594A (en) * | 2018-10-17 | 2019-01-11 | 中国科学院生态环境研究中心 | The preparation and application of the efficient Fenton catalyst of core-shell type iron-carbon micro-electrolytic material |
| CN110252305A (en) * | 2019-03-05 | 2019-09-20 | 中国科学院生态环境研究中心 | Keep the preparation and application of the iron-carbon micro-electrolytic material of the long-acting catalytic activity of Fenton system |
| CN110560168A (en) * | 2019-09-30 | 2019-12-13 | 天津工业大学 | Core-shell hierarchical iron/copper bimetallic Fenton catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| MENG WU ET AL.: "Efficient activation of peroxymonosulfate and degradation of Orange G in iron phosphide prepared by pickling waste liquor", 《CHEMOSPHERE》 * |
| ZHAOQIAN YAN ET AL.: "Ni-FeP @carbon core–shell structure as advanced anode materials for superior lithium storage", 《APPLIED SURFACE SCIENCE》 * |
| 刘双柳等: "纳米铜复合材料催化还原染料废水的研究", 《中国环境科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351445A (en) * | 2023-02-28 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
| CN116351445B (en) * | 2023-02-28 | 2024-05-10 | 齐鲁工业大学(山东省科学院) | Core-shell phosphating zero-valent iron material and preparation method and application thereof |
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