CN115193449A - Porous iron-based catalyst and preparation method thereof - Google Patents
Porous iron-based catalyst and preparation method thereof Download PDFInfo
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- CN115193449A CN115193449A CN202210800055.5A CN202210800055A CN115193449A CN 115193449 A CN115193449 A CN 115193449A CN 202210800055 A CN202210800055 A CN 202210800055A CN 115193449 A CN115193449 A CN 115193449A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 39
- 235000009496 Juglans regia Nutrition 0.000 claims abstract description 34
- 235000020234 walnut Nutrition 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052595 hematite Inorganic materials 0.000 claims abstract description 25
- 239000011019 hematite Substances 0.000 claims abstract description 25
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 25
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 21
- 239000011707 mineral Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000007493 shaping process Methods 0.000 claims abstract description 19
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 14
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 241000758789 Juglans Species 0.000 claims description 33
- 239000002351 wastewater Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000001413 cellular effect Effects 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000004480 active ingredient Substances 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 240000007049 Juglans regia Species 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000010248 power generation Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The application provides a porous iron-based catalyst and a preparation method thereof, wherein the method comprises the steps of mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio to obtain an iron-based mixture; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body; and sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst. The porous iron-based catalyst prepared by the method has more surface pores, the active ingredients of the catalyst are uniformly distributed, no agglomeration oxidation occurs, the Fenton catalytic reaction is met, and the catalyst material in the tubular Fenton reactor is convenient to replace regularly.
Description
Technical Field
The application relates to the technical field of Fenton catalyst preparation, in particular to a porous iron-based catalyst and a preparation method thereof.
Background
The industrial waste water treatment process relates to Fenton oxidation pretreatment process, and utilizes Fe 2+ And OH oxidation, so that organic matter of the refractory macromolecules is broken into small molecules and finally oxidized and decomposed into inorganic matter. In order to promote the reaction better, the Fenton reaction is improved by means of a Fenton catalyst, so that the catalytic effect and the utilization rate of the catalyst are improved, and the oxidative degradation energy of organic matters is obviously enhanced.
The existing Fenton catalyst has the defects of small reaction contact area, low reaction efficiency, granular, powdery or shaving catalyst structure, and inconvenient replacement of catalyst materials in a reactor because the shape of the catalyst cannot adapt to a tubular Fenton reactor well.
Disclosure of Invention
In view of the problems, the present application is proposed to provide a porous iron-based catalyst and a method for preparing the same, which overcome or at least partially solve the problems, comprising:
a method for preparing a porous iron-based catalyst for reacting with wastewater of refractory organics in a tubular reactor, comprising the steps of:
mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio to obtain an iron-based mixture;
mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body;
baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body;
and sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst.
Preferably, the step of baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body comprises:
preparing the honeycomb porous sponge body into a shape corresponding to the inside of the tubular Fenton reactor, and baking for 10-15 hours at 95-110 ℃ to obtain the honeycomb sponge shaping body.
Preferably, the step of sintering the honeycomb porous sponge shaped body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst comprises:
and (3) sintering the honeycomb sponge shaping body in an oxygen-free container at 400-450 ℃ for 3-4h to obtain the porous iron-based catalyst.
Preferably, the step of mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt ore powder according to a first preset mass ratio to obtain the iron-based mixture includes:
according to the following steps of 1:3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder according to a mass ratio to obtain the iron-based mixture.
Preferably, the first specified temperature is 95 ℃, or the first specified temperature is 105 ℃, or the first specified temperature is 110 ℃.
Preferably, the first specified time is 10h, or the first specified time is 12h, or the first specified time is 15h.
Preferably, the oxygen-free container is an oxygen-free muffle furnace.
Preferably, the second specified temperature is 400 ℃; or, the second specified temperature is 420 ℃; alternatively, the second specified temperature is 450 ℃.
Preferably, the second designated time is 3h; or, the second designated time is 3.5h; or, the second designated time is 4h.
The application also provides a porous iron-based catalyst prepared by the preparation method, which comprises coal-mine-shaped walnut shell powder and iron-based activated carbon adsorbed in pores of the walnut shell powder.
The application has the following advantages:
in the embodiment of the application, an iron-based mixture is obtained by mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body; and sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst. The porous iron-based catalyst prepared by the method has more surface pores, the active ingredients of the catalyst are uniformly distributed, and agglomeration oxidation does not occur, so that the Fenton catalytic reaction is met, and the catalyst material in the tubular Fenton reactor is conveniently replaced at regular intervals.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings required to be used in the description of the present application will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings may be obtained according to these drawings without inventive labor.
FIG. 1 is a flow chart illustrating the steps of a method for preparing a porous iron-based catalyst according to an embodiment of the present disclosure;
FIG. 2 is a schematic representation of a porous iron-based catalyst provided by an embodiment of the present application;
FIG. 3 is an SEM (scanning electron microscope) image of a porous iron-based catalyst material provided in an embodiment of the present application;
FIG. 4 is another SEM image of a porous iron-based catalyst material provided in an embodiment of the present application;
FIG. 5 is a schematic structural diagram of an apparatus for improving the efficiency of industrial wastewater treatment by photovoltaic electric heating energy according to an embodiment of the present application;
fig. 6 is a schematic structural diagram of a tubular reactor according to an embodiment of the present application.
The reference numbers in the drawings of the specification are as follows:
1. a photovoltaic power generation system; 2. an air source heat pump system; 3. a tubular reactor; 301. a catalytic inner zone; 302. a heat exchange outer zone; 31. a catalyst support layer; 32. a heat exchange tube; 321. a water inlet of the heat exchange tube; 322. a water outlet of the heat exchange tube; 33. a wastewater inlet; 34. a wastewater outlet; 35. a load-bearing column; 36. detaching the layer; 4. and (4) a regulating reservoir.
Detailed Description
In order to make the objects, features and advantages of the present application more comprehensible, the present application is described in further detail with reference to the accompanying drawings and the detailed description. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In any embodiment of the present invention, the porous iron matrix is used for reacting with wastewater of refractory organics in a tubular reactor 3, wherein the tubular reactor 3 is a part of a device for improving the efficiency of industrial wastewater treatment by photovoltaic-electric heating energy.
Specifically, referring to fig. 5, the equipment for improving the efficiency of industrial wastewater treatment by using photovoltaic electric heat energy is shown to comprise a photovoltaic power generation system 1, an air source heat pump system 2, a tubular reactor 3 and a regulating reservoir 4;
as shown in fig. 6, the tubular reactor 3 includes a reactor main body and a catalyst supporting layer 31 dividing the reactor main body into a catalytic inner zone 301 and a heat exchange outer zone 302, the catalyst supporting layer 31 is surrounded by a heat exchange tube 32, two ends of the heat exchange outer zone 302 are respectively provided with a wastewater inlet 33, and the top of the catalytic inner zone 301 is provided with a wastewater outlet 34; the tubular reactor 3 further comprises a disassembly layer 36 and a bearing column 35, wherein the disassembly layer 36 is arranged at the lower end of the wastewater outlet 34, and the bearing column 35 is arranged below the catalyst supporting layer 31;
the output end of the air source heat pump system 2 is connected with the water inlet 321 of the heat exchange tube, the water inlet 322 of the heat exchange tube is connected with one input end of the air source heat pump system 2, the other input end of the air source heat pump system 2 is connected with the output end of the photovoltaic power generation system 1, and the wastewater outlet 34 is connected with the regulating reservoir 4;
when the device works, the air source heat pump system 2 flows hot reflux water into the water inlet 321 of the heat exchange tube, and the hot reflux water flows back to the air source heat pump system 2 from the water outlet 322 of the heat exchange tube after heat exchange.
In this embodiment, the photovoltaic power generation system 1 includes a photovoltaic string, a power converter, a charge controller, and an energy storage device;
the photovoltaic group string is connected with the input end of the power converter, one output end of the power converter is connected with the air source heat pump system, the other output end of the power converter is connected with the input end of the charging controller, and the output end of the charging controller is connected with the energy storage system.
In the embodiment, the air source heat pump system 2 comprises an air energy exchanger, a compressor, a water heat exchanger and an oxidation pretreatment device;
the input end of the air energy exchanger is connected with the output end of the power converter, the output end of the air energy exchanger is connected with the input end of the compressor, the output end of the compressor is connected with one input end of the water heat exchanger, and the output end of the water heat exchanger is connected with the input end of the oxidation pretreatment device.
In this embodiment, the water inlet 321 of the heat exchange tube is connected to the output end of the oxidation pretreatment device, and the water outlet 322 of the heat exchange tube is connected to the other input end of the water heat exchanger.
In this embodiment, the wastewater inlet 33 is provided with a line mixer.
In this embodiment, the waste water outlet 34 is connected to the regulating reservoir 4.
Referring to fig. 1, a method for preparing a porous iron-based catalyst for reacting with wastewater of refractory organics in a tubular reactor according to an embodiment of the present disclosure is shown;
the method comprises the following steps:
s110, mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio to obtain an iron-based mixture;
s120, mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body;
s130, baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaping body;
s140, sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst.
In the embodiment of the application, an iron-based mixture is obtained by mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body; and sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst. The porous iron-based catalyst prepared by the method has more surface pores, the active ingredients of the catalyst are uniformly distributed, no agglomeration oxidation occurs, the Fenton catalytic reaction is met, and the catalyst material in the tubular Fenton reactor is convenient to replace regularly.
Next, a method for preparing a porous iron-based catalyst in the present exemplary embodiment will be further described.
And step S110, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder according to a first preset mass ratio to obtain an iron-based mixture.
In an embodiment of the present invention, the specific process of "mixing the walnut shell powder, the iron powder, the hematite powder and the nicrobite powder according to the first predetermined mass ratio to obtain the iron-based mixture" in step S110 can be further described with reference to the following description.
As described in the following steps, according to 1:3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder according to a mass ratio to obtain the iron-based mixture.
The iron powder is Fe 0 The hematite powder is Fe 3 O 4 The sulfur nickel cobalt mineral powder is (NiCo) 3 S 4 。
As an example, the walnut shell flour was ground into a flour and blended as per 1:3:3:2, uniformly mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder in a mass ratio, wherein in the process of mixing the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder by the walnut shell powder, part of the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder are adsorbed into pores of the walnut shell powder; wherein the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder are used as catalytic reactants.
And step S120, mixing the iron-based mixture and the kaolin according to a second preset mass ratio to obtain the honeycomb porous sponge.
In an embodiment of the present invention, the specific process of "mixing the iron-based mixture and kaolin according to the second predetermined mass ratio to obtain the honeycomb porous sponge" in step S120 can be further described with reference to the following description.
As an example, the iron-based mixture and the kaolin are mixed according to a second preset mass ratio, and after being uniformly mixed, a honeycomb porous sponge body is manufactured; the kaolin is mainly used for bonding and fixing the walnut shell powder to form a shape.
As an example, the second preset mass ratio is 1:8 to 10.
And step S130, baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body.
In an embodiment of the present invention, the specific process of "baking the cellular porous sponge at the first designated temperature for the first designated time to obtain the cellular porous sponge shaped body" in step S130 can be further described with reference to the following description.
Preparing the honeycomb porous sponge body into a shape corresponding to the inside of the tubular Fenton reactor, and baking the honeycomb porous sponge body at the temperature of 95-110 ℃ for 10-15 hours to obtain the honeycomb sponge shaped body.
As an example, after the honeycomb porous sponge body is prepared into a cylindrical structure suitable for a tubular reactor, the honeycomb porous sponge body is dried, dehydrated and shaped.
As an example, the first designated temperature may be 95 ℃, 97 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃ and 110 ℃, which may be selected according to actual conditions.
As an example, the first designated time may be 10h, 11h, 12h, 13h, 14h and 15h, which may be selected according to actual situations.
And step S140, sintering the honeycomb porous sponge shaped body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst.
In an embodiment of the present invention, the specific process of sintering the honeycomb porous sponge shaped body at the second specified temperature for the second specified time to obtain the porous iron-based catalyst in step S140 can be further described with reference to the following description.
And (2) placing the honeycomb sponge shaping body in an oxygen-free container at 400-450 ℃ for sintering for 3-4h to obtain the porous iron-based catalyst.
In this embodiment, the oxygen-free vessel is an oxygen-free muffle furnace.
As an example, the cellular porous sponge shaped body obtained after shaping is placed in an oxygen-free muffle furnace with the temperature of 400-450 ℃ for burningAnd (3) sintering for 3-4h, converting the walnut shell powder into novel iron-based-activated carbon in the sintering process, forming a porous structure, improving the catalytic capability of the catalyst, increasing the porosity of the iron-based catalyst along with gas overflow and volume change in the sintering process of the walnut shell powder, and preparing the porous iron-based catalyst to obtain the porous iron-based catalyst material shown in the figure 2. After the preparation, the porous iron-based catalyst is placed in a tubular reactor and reacts with wastewater in a contact way, and after reacting for a period of time, the catalyst material in the tubular reactor is replaced regularly. The porous structure of the porous iron-based catalyst has larger specific surface, can be better contacted with wastewater, improves the reaction efficiency, is prepared into a cylindrical structure suitable for a tubular reactor, and is convenient for catalyst replacement. Hematite powder (Fe) in the course of reaction 3 O 4 ) Sulfur nickel cobalt ore powder ((NiCo) 4 ) Slow precipitation of Fe 2+ /Fe 3+ And H 2 O 2 The Fenton reaction takes place, iron powder (Fe) 0 ) Can directly react with refractory substances in the wastewater and can also contact with Fe 3+ Post production of Fe 2+ The reaction is promoted, and a high-efficiency porous iron-based catalyst material is formed, and as can be seen from SEM images of the porous iron-based catalyst material shown in figures 3 and 4, the porous iron-based catalyst has more surface pores, the active ingredients of the catalyst are uniformly distributed, and no agglomeration oxidation occurs.
As an example, the second designated temperature may be 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃ and 450 ℃, which may be selected according to actual conditions.
As an example, the second designated time may be 3h, 3.2h, 3.5h, 3.6h, 3.8h and 4h, which may be selected according to actual situations.
The application also provides a porous iron-based catalyst which is prepared by the preparation method of the porous iron-based catalyst and comprises coal-mine-shaped walnut shell powder and iron-based activated carbon adsorbed in pores of the walnut shell powder.
As an example, walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder contained in the porous iron-based catalyst are used as catalytic reactants, kaolin is mainly used for binding and fixing to form a fixed shape, in the process of mixing the walnut shell powder with the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder, part of the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder are adsorbed into pores of the walnut shell powder, novel iron-based active carbon is formed in the sintering process, the catalytic capability of the catalyst is improved, and the porosity of the iron-based catalyst is increased along with gas overflow and volume change in the sintering process of the walnut shell powder, so that the porous iron-based catalyst is prepared. The content of the main catalytic reactant of the obtained porous iron-based catalyst is 85-95%, the effective component is high, the reaction loss is low, the porous structure is suitable for a tubular Fenton reactor, and the catalyst material in the reactor is convenient to replace.
Example 1
According to the following steps: 3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder in a mass ratio to obtain an iron-based mixture; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; preparing the honeycomb porous sponge body into a shape corresponding to the interior of the tubular Fenton reactor, and baking the honeycomb porous sponge body for 10 hours at 95 ℃ to obtain the honeycomb sponge shaping body; and (3) sintering the honeycomb sponge shaping body in an oxygen-free container at 400 ℃ for 3h to obtain the porous iron-based catalyst.
The porous iron-based catalyst prepared in example 1 was placed in the catalytic inner zone 301 of the tubular reactor 3. The photovoltaic power generation system generates power all year round and supplies power to an air source heat pump system, the air source heat pump system 2 exchanges heat with a heat source until backflow water flows into a tubular reactor 3, the tubular reactor 3 controls the optimal water temperature entering the tubular reactor 3 after determining the optimal temperature of refractory organic matters through tests, wastewater adjusts acidity and adds H 2 O 2 The solution enters the heat exchange outer zone 302 of the tubular reactor 3 from the wastewater inlet 33 at the upper part of the reactor, enters the catalysis inner zone 301 after the temperature is raised, enters the regulating tank 4 after the reaction of the wastewater and the porous iron-based catalyst is finished, regulates the alkalinity, precipitates and enters the next process (biochemical stage).
After the reaction of the porous iron-based catalyst with the wastewater is completed, the porous iron-based catalyst is replaced by detaching layer 36.
The reaction temperature is increased, the Fenton advanced oxidation equipment has obvious effect, the molecular collision rate of the porous iron-based catalyst is increased due to the increase of the temperature, OH is generated, the contact probability of OH and organic matters is increased, and the oxidative degradation effect is improved.
Example 2
According to the following steps of 1:3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder according to the mass ratio to obtain an iron-based mixture; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; preparing the honeycomb porous sponge body into a shape corresponding to the interior of the tubular Fenton reactor, and baking the honeycomb porous sponge body at 105 ℃ for 12 hours to obtain the honeycomb sponge shaping body; and (3) placing the honeycomb sponge shaping body in an oxygen-free container at 420 ℃ for sintering for 3.5 hours to obtain the porous iron-based catalyst.
The reaction of the porous iron-based catalyst prepared in example 2 in the catalytic inner zone 301 is identical to that of example 1 and will not be described herein.
Example 3
According to the following steps of 1:3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder in a mass ratio to obtain an iron-based mixture; mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body; preparing the honeycomb porous sponge body into a shape corresponding to the interior of the tubular Fenton reactor, and baking the honeycomb porous sponge body for 15 hours at 110 ℃ to obtain the honeycomb sponge shaping body; and (3) placing the honeycomb sponge shaping body in an oxygen-free container at 450 ℃ for sintering for 4h to obtain the porous iron-based catalyst.
The reaction of the porous iron-based catalyst prepared in example 3 in the catalytic inner zone 301 is identical to that of example 1 and will not be described herein.
Finally, it should also be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising one of \ 8230; \8230;" does not exclude the presence of additional like elements in a process, method, article, or terminal device that comprises the element.
The porous iron-based catalyst and the preparation method thereof provided by the present application are described in detail above, and the principle and the embodiment of the present application are explained in the present application by applying specific examples, and the description of the above examples is only used to help understanding the method and the core concept of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. A method for preparing a porous iron-based catalyst for reacting with wastewater of refractory organics in a tubular reactor, comprising the steps of:
mixing walnut shell powder, iron powder, hematite powder and sulfur nickel cobalt mineral powder according to a first preset mass ratio to obtain an iron-based mixture;
mixing the iron-based mixture and kaolin according to a second preset mass ratio to obtain a honeycomb porous sponge body;
baking the honeycomb porous sponge body at a first specified temperature for a first specified time to obtain a honeycomb porous sponge shaped body;
and sintering the honeycomb porous sponge shaping body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst.
2. The method of claim 1, wherein the step of baking the cellular porous sponge body at a first specified temperature for a first specified time to obtain a cellular porous sponge shaped body comprises:
preparing the honeycomb porous sponge body into a shape corresponding to the interior of the tubular Fenton reactor, and baking for 10-15h at 95-110 ℃ to obtain the honeycomb sponge shaping body.
3. The method of claim 2, wherein the step of sintering the honeycomb porous sponge shaped body at a second specified temperature for a second specified time to obtain the porous iron-based catalyst comprises:
and (3) sintering the honeycomb sponge shaping body in an oxygen-free container at 400-450 ℃ for 3-4h to obtain the porous iron-based catalyst.
4. The method according to claim 1, wherein the step of mixing walnut shell powder, iron powder, hematite powder and volkobal ore powder in a first predetermined mass ratio to obtain an iron-based mixture comprises:
according to the following steps of 1:3:3:2, mixing the walnut shell powder, the iron powder, the hematite powder and the sulfur nickel cobalt mineral powder according to a mass ratio to obtain the iron-based mixture.
5. The method of claim 2, wherein the first specified temperature is 95 ℃, or the first specified temperature is 105 ℃, or the first specified temperature is 110 ℃.
6. The method of claim 2, wherein the first specified time is 10 hours, or wherein the first specified time is 12 hours, or wherein the first specified time is 15 hours.
7. The method of claim 3, wherein the oxygen-free vessel is an oxygen-free muffle.
8. The method of claim 3, wherein the second specified temperature is 400 ℃; or, the second specified temperature is 420 ℃; alternatively, the second specified temperature is 450 ℃.
9. The method of claim 3, wherein the second designated time is 3 hours; or, the second designated time is 3.5h; or, the second designated time is 4h.
10. A porous iron-based catalyst prepared by the preparation method according to any one of claims 1 to 9, comprising walnut shell flour in a coal mine form and iron-based activated carbon adsorbed in pores of the walnut shell flour.
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