CN115069257A - Method for preparing denitration catalyst by utilizing Fenton iron mud - Google Patents
Method for preparing denitration catalyst by utilizing Fenton iron mud Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000011282 treatment Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims description 26
- 238000000967 suction filtration Methods 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 238000007605 air drying Methods 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003546 flue gas Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 5
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000004571 lime Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 229910002588 FeOOH Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention relates to a method for preparing a denitration catalyst by utilizing Fenton iron mud. The preparation method comprises the following steps: iron mud pretreatment, primary calcination, high-temperature water washing dealkalization, deep combined dealkalization and secondary calcination. The primary calcination is to remove free water and crystal water of the iron mud, so that the iron mud is subjected to chemical and phase reaction, and the dealkalization rate of the subsequent process is improved; removing free alkali and partial chemically combined alkali in the Fenton iron mud by washing with high-temperature water and dealkalizing; deep combined dealkalization and high-temperature and high-pressure lime dealkalization method and CO 2 Removing chemically combined alkali in Fenton iron mud in a three-phase system by using a dealkalization method; secondary calcination treatment to Fe (OH) at ordinary temperature 3 And FeOOH into Fe with high catalytic activity 2 O 3 And improve the thermal stability thereof. Free alkali and large alkali in iron mud by double dealkalization treatmentAnd part of chemical combination alkali is removed, so that the phenomenon that the high-degree alkali blocks the pore diameter and occupies active sites to further influence the catalytic activity is effectively avoided. The Fenton iron mud denitration catalyst prepared finally has excellent denitration efficiency.
Description
Technical Field
The invention belongs to the technical field of environmental protection and industrial hazardous waste resource utilization, and particularly relates to a method for preparing a denitration catalyst by utilizing Fenton iron mud.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Nitrogen Oxides (NO) emitted by industrial production x ) Is one of main atmospheric pollutants, and is an important source for causing atmospheric pollution problems such as haze, photochemical smog and the like. The SCR technology is the most mature industrial denitration technology at present, and has the advantages of low cost, high efficiency and the like. The development of high-efficiency catalysts is one of the keys of the SCR technology, and the commercial vanadium-titanium catalyst widely applied at present cannot completely meet the requirements of various industries due to high cost, strong toxicity and high reaction temperature, so that the large-scale popularization of the SCR technology is restricted. Therefore, the development of new SCR catalysts with low cost, high activity and low temperature window is urgent.
The Fenton iron mud is industrial hazardous waste generated after industrial organic wastewater is treated by a Fenton technology. It contains a large amount of heavy metal elements (45-70%) such as iron, aluminum, manganese and the like, and if the heavy metal elements are directly discharged, the heavy metal elements can cause serious harm to the environment. At present, Fenton iron mud is mainly treated by incineration and landfill and cement-based curing, but secondary pollution is easily caused in a harmless treatment process, and waste of resources such as iron, aluminum and the like is caused. The Fenton iron mud contains a large amount of elements such as iron, aluminum, silicon and the like, and has potential for preparing an iron-based denitration catalyst. However, the existence of high alkali in the iron mud not only easily causes the high-temperature sintering of the catalyst, but also blocks the pore structure, reduces the surface area and further influences the denitration efficiency of the catalyst. The dealkalization by lime method has good dealkalization effect on alkali-containing sludge, and the lime is easy to produce, has lower cost and extremely high application value, and CO 2 The dealkalization method also shows better effect. If the Fenton iron mud and the catalyst can be jointly used for dealkalizing the Fenton iron mud, the chemical bound alkali in the iron mud can be effectively removed, the aim of deep dealkalization is fulfilled, and the catalytic activity of the catalyst is effectively improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing a denitration catalyst by using Fenton iron mud, which is characterized in that free alkali and chemically combined alkali in the Fenton iron mud are removed in a targeted manner through continuous constant-temperature water washing treatment, and then a lime replacement dealkalization method is used as a main body and CO is used for removing alkali 2 The dealkalization method is to assist the two methods to carry out dealkalization treatment on the Fenton iron mud under the conditions of temperature rise and pressure rise. The deep dealkalization treatment can effectively dredge the pore structure of the iron mud, increase the surface area, avoid high-temperature sintering and improve the denitration efficiency of the Fenton iron mud catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided a method for preparing a denitration catalyst using fenton iron mud, comprising the steps of:
(1) iron sludge pretreatment
Dehydrating the original Fenton iron mud, and crushing and screening the dehydrated Fenton iron mud to obtain Fenton iron mud powder;
(2) primary calcination
Placing the pretreated Fenton iron mud powder in a muffle furnace for high-temperature calcination treatment to obtain a Fenton iron mud denitration catalyst precursor;
(3) high-temperature water washing dealkalization
Heating deionized water, adding a Fenton iron mud denitration catalyst precursor, uniformly stirring to obtain a suspension, and then carrying out microwave heating treatment; after the reaction is finished, carrying out suction filtration, washing and drying on the suspension to obtain a precipitate;
(4) deep combined dealkalization
Uniformly mixing the precipitate, CaO and deionized water, adding into a three-phase reactor, and introducing CO 2 Gas, raising the reaction temperature and the reaction pressure, and adjusting the stirring speed; after the reaction is finishedCarrying out suction filtration, washing and drying to obtain a secondary precipitate;
(5) second calcination
And (4) placing the secondary precipitate in a muffle furnace for high-temperature calcination treatment again to obtain the Fenton iron mud denitration catalyst.
The water content of the original Fenton iron mud is 95-97%.
The high-temperature calcination temperature in the step (2) is 350-500 ℃, preferably 400-450 ℃, and the high-temperature calcination time is 30-120min, preferably 50-90 min.
And (4) after microwave heating treatment in the step (3), adding the suspension into a constant-temperature suction filtration device for suction filtration, continuously washing with high-temperature deionized water at 70-90 ℃, and drying the obtained precipitate in a forced air drying oven for 10-12 hours after washing.
The solid-to-liquid ratio of the suspension in the step (3) is 1: 4-12, preferably 1: 7-9.
The microwave power in the microwave reactor in the step (3) is 300-600W, preferably 400-500W; the heating temperature is 40-80 ℃; preferably 55-65 ℃; the stirring speed is 200-800 r/min; preferably 400-600 r/min; the reaction time is 30-90 min; preferably 60-80 min.
The content of CaO (the mass fraction of CaO in the precipitate) added in the step (3) is 3-8%, preferably 5-6%.
The pressure in the three-phase reactor in the step (3) is 3-7 MPa; preferably 5-6 MPa; the reaction temperature is 60-90 ℃; preferably 70-80 ℃; the reaction time is 60-120 min; preferably 80-100 min; the stirring speed is 500-1200 r/min; preferably 600-; CO2 2 The flow rate is 100-300 mL/min; preferably 200 and 250 mL/min.
The washing time in the step (3) is 20-90 min; preferably 40-60 min. The washing temperature is 20-60 ℃; preferably from 30 to 50 ℃. The stirring speed is 50-400 r/min; preferably 100-.
In the step (4), after the reaction is finished, the suspension is added into the constant-temperature suction filtration device again for suction filtration treatment, high-temperature deionized water is also adopted for full and continuous washing treatment, and after the reaction is finished, the obtained precipitate is placed in the air-blast drying oven again for drying for 10-12 hours.
The high-temperature calcination temperature in the step (5) and the step (2) is the same, and the secondary calcination time is 360 min-.
The continuous water washing temperature and time in the step (3) and the step (4) are the same.
In a second aspect of the invention, the fenton iron mud denitration catalyst prepared by the method is provided.
In a third aspect of the invention, the Fenton iron mud denitration catalyst prepared by the method is applied to the field of flue gas denitration;
preferably, the reaction temperature window of the fenton iron mud denitration catalyst is 300-450 ℃, and the denitration efficiency is over 90% in the temperature window.
The beneficial effects of the invention are:
(1) the Fenton iron mud is subjected to double calcination treatment, so that free water, crystal water and volatile components in the iron mud are removed in a short calcination time, chemical and phase reactions occur, the dissolution of a sodium phase is increased, and the dealkalization rate in the subsequent high-temperature water washing and combined dealkalization processes is improved. The secondary calcination time is longer to ensure that the Fe (OH) at normal temperature 3 And FeOOH into Fe with high catalytic activity 2 O 3 The crystal phase structure is fixed, and the thermal stability and the chemical stability of the catalyst are ensured.
(2) The invention pertinently adopts a continuous high-temperature water washing method to carry out pretreatment on Fenton iron mud suspension, and removes CaSO which is insoluble in acid and slightly soluble in water in Fenton iron mud 4 And increasing CaSO by increasing water temperature 4 The solubility of the sodium hydroxide further improves the dealkalization rate and lays a cushion for subsequent deep dealkalization. And use microwave heating to handle fenton iron mud, effectively avoided the turbid liquid local overheat phenomenon to appear, promote rate of heating and make its reaction even, and can effectively reduce the energy consumption.
(3) Ca with strong exchange capacity formed by dissolving CaO in water at high temperature and high pressure through a three-phase reactor 2+ Replacing part of K + 、Na + Generating soluble potassium and sodium salts and introducing CO simultaneously 2 By means of CO 2 The carbonic acid dissolved in water is subjected to combined deep dealkalization, and the generated soluble salt can be removed through subsequent continuous high-temperature water washing.
(4) The invention utilizes water, lime and CO 2 The dealkalization treatment is carried out on the Fenton iron mud, so that the dealkalization cost and the whole energy consumption are effectively reduced, the secondary pollution is not generated, and the effective removal of the chemically combined alkali in the Fenton iron mud is realized through the double dealkalization and the combined dealkalization. Further increased the surface area of catalyst, dredged pore structure, effectively promoted the denitration efficiency of fenton's iron mud catalyst.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a flow chart of a process for preparing a fenton iron mud denitration catalyst.
Fig. 2 is a graph showing the denitration efficiency of the fenton iron sludge denitration catalyst.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
As shown in the flow chart of the preparation of fenton iron mud denitration catalyst in fig. 1.
The original Fenton iron mud with the water content of 95-97% is dehydrated, and the dehydrated Fenton iron mud is smashed and screened to obtain Fenton iron mud powder.
20g of the pretreated fenton iron mud powder is placed in a muffle furnace to be calcined at 400 ℃ for 50min, and after the Fenton iron mud powder is cooled to room temperature, the weight ratio of the Fenton iron mud powder to the air is 1: and 7, adding deionized water at 40 ℃ into the obtained Fenton iron mud denitration catalyst precursor. And then placing the suspension in a microwave reactor for microwave heating treatment, setting the microwave power at 500W, the heating temperature at 70 ℃, the stirring speed at 400r/min and the reaction time at 70 min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device, continuously washing with deionized water at a high temperature of 50 ℃ for 40min, and after the washing is finished, placing the precipitate in a forced air drying oven for drying for 10 h.
10g of the precipitate and 5% CaO were weighed into a beaker and mixed as 1: 7, adding deionized water into the mixture according to the solid-liquid ratio, uniformly mixing the deionized water and the deionized water, adding the mixture into a three-phase reactor, and then introducing CO into the three-phase reactor 2 A gas. Setting the pressure in the three-phase reactor to be 5.5MPa, the reaction temperature to be 80 ℃, the reaction time to be 90min, the stirring speed to be 600r/min, CO 2 The flow rate was 250 mL/min. And after the reaction is finished, adding the suspension into the constant-temperature suction filtration device again for suction filtration treatment, wherein the same parameters are adopted in the two water washing treatments. After the water washing, the obtained precipitate was dried again in a forced air drying oven for 10 h. And (3) placing the dried secondary precipitate in a muffle furnace to be calcined for 300min at a high temperature of 400 ℃ to obtain the Fenton iron mud denitration catalyst A.
Example 2
The original Fenton iron mud with the water content of 95-97% is dehydrated, and the dehydrated Fenton iron mud is smashed and screened to obtain Fenton iron mud powder.
20g of the pretreated fenton iron mud powder is placed in a muffle furnace to be calcined at 450 ℃ for 60min, and after the Fenton iron mud powder is cooled to room temperature, the weight ratio of the Fenton iron mud powder to the air is 1: and 7, adding deionized water at 40 ℃ into the obtained Fenton iron mud denitration catalyst precursor. And then placing the suspension in a microwave reactor for microwave heating treatment, setting the microwave power to be 400W, the heating temperature to be 55 ℃, the stirring speed to be 400r/min and the reaction time to be 70 min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device, continuously washing for 45min by using high-temperature deionized water at 30 ℃, and after the washing is finished, placing the precipitate in a forced air drying oven for drying for 10 h.
10g of the precipitate and 6% CaO were weighed into a beaker and mixed as 1: 7, adding deionized water, mixing uniformly, adding into a three-phase reactor, and introducing CO2 gas. The pressure in the three-phase reactor is set to be 5.5MPa, the reaction temperature is 80 ℃, the reaction time is 90min, the stirring speed is 600r/min, and the flow of CO2 is 200 mL/min. And after the reaction is finished, adding the suspension into the constant-temperature suction filtration device again for suction filtration treatment, wherein the same parameters are adopted in the two water washing treatments. After the water washing, the obtained precipitate was dried again in a forced air drying oven for 10 h. And (3) placing the dried secondary precipitate in a muffle furnace to be calcined for 330min at the high temperature of 450 ℃ to obtain the Fenton iron mud denitration catalyst B.
Example 3
The original Fenton iron mud with the water content of 95-97% is dehydrated, and the dehydrated Fenton iron mud is smashed and screened to obtain Fenton iron mud powder.
20g of the pretreated fenton iron mud powder is placed in a muffle furnace to be calcined at 450 ℃ for 60min, and after the Fenton iron mud powder is cooled to room temperature, the weight ratio of the Fenton iron mud powder to the air is 1: and 8, adding deionized water at 70 ℃ into the obtained Fenton iron mud denitration catalyst precursor according to the solid-liquid ratio. And then placing the suspension in a microwave reactor for microwave heating treatment, setting the microwave power to be 500W, the heating temperature to be 60 ℃, the stirring speed to be 500r/min and the reaction time to be 70 min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device, continuously washing for 50min by using high-temperature deionized water at 40 ℃, and after the washing is finished, placing the precipitate in a forced air drying oven for drying for 10 h.
10g of the precipitate and 6% CaO were weighed into a beaker and mixed as 1: 7, adding deionized water, mixing uniformly, adding into a three-phase reactor, and introducing CO2 gas. The pressure in the three-phase reactor is set to be 6MPa, the reaction temperature is 80 ℃, the reaction time is 90min, the stirring speed is 700r/min, and the flow of CO2 is 250 mL/min. And after the reaction is finished, adding the suspension into the constant-temperature suction filtration device again for suction filtration treatment, wherein the same parameters are adopted in the two water washing treatments. After the water washing, the obtained precipitate was dried again in a forced air drying oven for 12 h. And (3) placing the dried secondary precipitate in a muffle furnace to be calcined for 300min at the high temperature of 450 ℃ to obtain the Fenton iron mud denitration catalyst C.
The iron mud catalysts a-C of examples 1-3 were selected for denitration efficiency testing and dealkalization rate calculation, and from the test and analysis data, it was known (as shown in table 1 and fig. 2): the combined deep dealkalization treatment can ensure that the dealkalization rate of Fenton iron mud exceeds 80 percent and can reach 87 percent at most; the prepared Fenton iron mud catalyst shows good catalytic activity, and the denitration efficiency can reach more than 90% in the reaction temperature range of 315 plus 430 ℃.
TABLE 1 removal rate table for alkaline substances in Fenton's iron sludge by combined dealkalization
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a denitration catalyst by utilizing Fenton iron mud is characterized by comprising the following steps:
(1) iron sludge pretreatment
Dehydrating the original Fenton iron mud, and crushing and screening the dehydrated Fenton iron mud to obtain Fenton iron mud powder;
(2) primary calcination
Placing the pretreated Fenton iron mud powder in a muffle furnace for high-temperature calcination treatment to obtain a Fenton iron mud denitration catalyst precursor;
(3) high-temperature water washing dealkalization
Heating deionized water, adding a Fenton iron mud denitration catalyst precursor, uniformly stirring to obtain a suspension, and then carrying out microwave heating treatment; after the reaction is finished, carrying out suction filtration, washing and drying on the suspension to obtain a precipitate;
(4) deep combined dealkalization
Uniformly mixing the precipitate, CaO and deionized water, adding into a three-phase reactor, and introducing CO 2 Gas, raising the reaction temperature and the reaction pressure, and adjusting the stirring speed; after the reaction is finished, carrying out suction filtration, washing and drying to obtain a secondary precipitate;
(5) second calcination
And (4) placing the secondary precipitate in a muffle furnace for high-temperature calcination treatment again to obtain the Fenton iron mud denitration catalyst.
2. The method according to claim 1, wherein the original Fenton iron mud has a water content of 95-97%.
3. The method as claimed in claim 1, wherein the high temperature calcination temperature in step (2) is 350-.
4. The method according to claim 1, wherein the solid-to-liquid ratio of the suspension in the step (3) is preferably 1: 4-12, preferably 1: 7-9;
preferably, the content of CaO added in the step (3) is 3 to 8%, preferably 5 to 6%, based on the total mass of the precipitate.
5. The method according to claim 1, wherein after the microwave heating treatment in the step (3), the suspension is added into a constant-temperature suction filtration device for suction filtration and is subjected to continuous water washing treatment by using high-temperature deionized water at 70-90 ℃, and after the water washing is finished, the obtained precipitate is dried in a forced air drying oven for 10-12 hours;
preferably, the microwave power in the microwave reactor in the step (3) is 300-600W, preferably 400-500W; the heating temperature is 40-80 ℃; preferably 55-65 ℃; the stirring speed is 200-800 r/min; preferably 400-; the reaction time is 30-90 min; preferably 60-80 min;
preferably, the pressure in the three-phase reactor in the step (3) is 3-7 MPa; preferably 5-6 MPa; the reaction temperature is 60-90 ℃; preferably 70-80 ℃; the reaction time is 60-120 min; preferably 80-100 min; the stirring speed is 500-1200 r/min; preferably 600-; CO2 2 The flow rate is 100-300 mL/min; preferably 200 and 250 mL/min;
preferably, the water washing time in the step (3) is 20-90 min; preferably 40-60 min; the washing temperature is 20-60 ℃; preferably 30-50 ℃; the stirring speed is 50-400 r/min; preferably 100-.
6. The method according to claim 5, wherein in the step (4), after the reaction is finished, the suspension is added into the constant-temperature suction filtration device again for suction filtration treatment, high-temperature deionized water is also adopted for full and continuous water washing treatment, and after the reaction is finished, the obtained precipitate is dried in the air-blast drying oven again for 10-12 hours.
7. The method as claimed in claim 1, wherein the high temperature calcination temperature in step (5) and step (2) is the same, and the secondary calcination time is 240-360min, preferably 300-330 min.
8. The method according to claim 1, wherein the continuous water washing temperature and time in the step (3) and the step (4) are the same.
9. Fenton's iron mud denitration catalyst prepared according to the method of any one of the preceding claims.
10. The Fenton iron mud denitration catalyst of claim 9 is applied to the field of flue gas denitration;
preferably, the reaction temperature window of the fenton iron mud denitration catalyst is 300-450 ℃, and the denitration efficiency is over 90% in the temperature window.
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