CN115069257B - Method for preparing denitration catalyst by Fenton iron mud - Google Patents
Method for preparing denitration catalyst by 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 176
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000011282 treatment Methods 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 23
- 238000000967 suction filtration Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 238000003837 high-temperature calcination Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 208000005156 Dehydration Diseases 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 4
- 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
- 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
- 239000000126 substance Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 229910002588 FeOOH Inorganic materials 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 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
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 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
- 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
- 238000011161 development Methods 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000013021 overheating 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to a method for preparing a denitration catalyst by Fenton iron mud. The preparation method comprises the following steps: pretreating iron mud, performing primary calcination, eluting alkali with high temperature water, deeply combining alkali removal 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 chemical combined alkali in Fenton iron mud by eluting alkali at high temperature; high-temperature high-pressure lime dealkalization method and CO combined by deep combined dealkalization 2 The dealkalization method is used for removing chemically combined alkali in Fenton iron mud in a three-phase system; the secondary calcination treatment leads to Fe (OH) at normal temperature 3 And FeOOH to Fe with high catalytic activity 2 O 3 And improves its thermal stability. Free alkali and most of chemically combined alkali in the iron mud are removed through double dealkalization treatment, so that the phenomenon that the aperture is blocked by high alkali and active sites are occupied, and the catalytic activity is influenced is effectively avoided. The Fenton iron mud denitration catalyst finally prepared 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 the 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 admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Nitrogen Oxides (NO) discharged from industrial production x ) Is one of main atmospheric pollutants and is an important source for causing the problems of atmospheric pollution 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 the high-efficiency catalyst is one of the keys of the SCR technology, and the commercial vanadium-titanium catalyst widely applied at present has high cost, strong toxicity and higher reaction temperature, so that the requirements of various industries cannot be completely met, and the large-scale popularization of the SCR technology is restricted. Therefore, there is an urgent need to develop a novel SCR catalyst with low cost, high activity, and low temperature window.
Fenton iron mud is industrial hazardous waste generated after industrial organic wastewater is treated by Fenton technology. It contains a large amount of heavy metal elements (45-70%) such as iron, aluminum, manganese, etc., and if directly discharged, the heavy metal elements cause serious harm to the environment. At present, the Fenton iron mud is mainly disposed in a landfill and cement-based solidification mode after incineration, however, secondary pollution is very easy to cause in the harmless treatment process, and the waste of resources such as iron, aluminum and the like is caused. The Fenton iron mud has a great amount of iron, aluminum, silicon and other elements, and has the potential of preparing the iron-based denitration catalyst. However, the existence of high alkali in the iron mud not only can easily cause high-temperature sintering of the catalyst, but also can block the pore structure, reduce the surface area and further influence the denitration efficiency of the catalyst. The lime process dealkalization has good dealkalization effect on alkali-containing sludge, and lime is easy to produce, low in cost and extremely high in application value, and CO 2 The dealkalization method also shows better effect. If the Fenton iron mud can be treated by dealkalizing by combining the Fenton iron mud and the alkali, the chemically combined alkali in the iron mud can be effectively removed, the purpose of deep dealkalization is realized, and the catalytic activity of the catalyst is effectively improved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a denitration catalyst by utilizing Fenton iron mud, which comprises the steps of carrying out targeted removal on free alkali and chemically combined alkali in the Fenton iron mud through continuous constant-temperature water washing treatment, and then using a lime replacement dealkalization method as a main body and CO 2 The dealkalization method is to assist the combination of the two to dealkalize Fenton iron mud under the condition of heating and pressurizing. 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 above 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 mud pretreatment
Carrying out dehydration treatment on the original Fenton iron mud, and carrying out crushing and screening treatment on the dehydrated Fenton iron mud to obtain Fenton iron mud powder;
(2) Primary calcination
Placing the pretreated Fenton iron mud powder into a muffle furnace for high-temperature calcination treatment to obtain a Fenton iron mud denitration catalyst precursor;
(3) Eluting alkali with high temperature water
After 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, water washing and drying on the suspension to obtain a precipitate;
(4) Deep combined dealkalization
Mixing precipitate, caO and deionized water, adding into a three-phase reactor, and introducing CO 2 The gas, raise reaction temperature and reaction pressure, and regulate the stirring rate; after the reaction is finished, carrying out suction filtration, washing and drying to obtain a secondary precipitate;
(5) Secondary calcination
And (3) 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 50-90min.
And (3) after the microwave heating treatment in the step (3), adding the suspension into a constant-temperature suction filtration device for suction filtration, continuously washing with 70-90 ℃ high-temperature deionized water, and after the washing is finished, placing the obtained precipitate into a blast drying oven for drying for 10-12h.
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 200-800r/min; preferably 400-600r/min; the reaction time is 30-90min; preferably 60-80min.
The content of CaO added in the step (3) (the mass fraction of CaO is 3% -8%, preferably 5% -6%) of the precipitate.
The pressure in the three-phase reactor in the step (3) is 3-7MPa; preferably 5-6MPa; the reaction temperature is 60-90 ℃; preferably 70-80 ℃; the reaction time is 60-120min; preferably 80-100min; the stirring speed is 500-1200r/min; preferably 600-800r/min; CO 2 The flow is 100-300mL/min; preferably 200-250mL/min.
The water washing time in the step (3) is 20-90min; preferably 40-60min. The water washing temperature is 20-60 ℃; preferably 30-50 ℃. Stirring at a speed of 50-400r/min; preferably 100-200r/min.
In the step (4), after the reaction is finished, adding the suspension into a constant-temperature suction filtration device again for suction filtration treatment, adopting high-temperature deionized water to perform full continuous water washing treatment, and after the reaction is finished, placing the obtained precipitate into a blast drying oven again for drying for 10-12h.
The high-temperature calcination temperature in the step (5) and the step (2) is the same, and the secondary calcination time is 240-360min, preferably 300-330min.
And (3) and (4) the continuous water washing temperature and time are the same.
In a second aspect of the invention, a Fenton iron mud denitration catalyst prepared by the method is provided.
In a third aspect of the invention, the application of the Fenton iron mud denitration catalyst prepared by the method in the field of flue gas denitration is provided;
preferably, the Fenton iron mud denitration catalyst has a reaction temperature window of 300-450 ℃, and the denitration efficiency exceeds 90% in the temperature window.
The beneficial effects of the invention are as follows:
(1) The Fenton iron mud is subjected to double calcination treatment, free water, crystal water and volatile matters in the iron mud are removed by one-time calcination in a short time, chemical reaction and phase reaction are carried out, the dissolution of 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 lead Fe (OH) at normal temperature 3 And FeOOH to Fe with high catalytic activity 2 O 3 Fix the crystal phase structure and ensure the thermal stability and chemical stability of the catalyst.
(2) The invention adopts a continuous high-temperature water washing method to pretreat Fenton iron mud suspension to remove CaSO which is difficult to dissolve in acid but slightly soluble in water in Fenton iron mud 4 And increase CaSO by increasing water temperature 4 The solubility of the product is further improved, and the product is used for laying a subsequent deep dealkalization. And the Fenton iron mud is treated by using microwave heating, so that the phenomenon of local overheating of the suspension is effectively avoided, the heating speed is increased, the reaction is uniform, and the energy consumption can be effectively reduced.
(3) The invention utilizes Ca with strong exchange capability formed by dissolving CaO in water under high temperature and high pressure through a three-phase reactor 2+ K of substituted part + 、Na + Generating soluble potassium and sodium salts and simultaneously introducing CO 2 By CO 2 The carbonic acid dissolved in water is combined with deep dealkalization, and the generated soluble salt can be removed by subsequent continuous high-temperature water washing.
(4) The invention utilizes water, lime and CO 2 Iron of ParafiltonThe sludge is subjected to dealkalization treatment, so that dealkalization cost and overall energy consumption are effectively reduced, secondary pollution is avoided, and the effective removal of chemically combined alkali in Fenton iron sludge is realized through double dealkalization and combined dealkalization. The surface area of the catalyst is further increased, the pore structure is dredged, and the denitration efficiency of the Fenton iron mud catalyst is effectively improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
Fig. 1 is a flow chart of the preparation of a Fenton iron mud denitration catalyst.
Fig. 2 is a graph of denitration efficiency of the Fenton iron mud denitration catalyst.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
As shown in the preparation flow chart of the Fenton iron mud denitration catalyst in fig. 1.
And (3) carrying out dehydration treatment on the original Fenton iron mud with the water content of 95-97%, and carrying out crushing and screening treatment on the dehydrated Fenton iron mud to obtain Fenton iron mud powder.
Taking 20g of pretreated Fenton iron mud powder, placing the powder into a muffle furnace, calcining at 400 ℃ for 50min, cooling to room temperature, and then carrying out the steps of 1:7 solid-to-liquid ratio adding deionized water at 40 ℃ into the Fenton iron mud denitration catalyst precursor. And then placing the suspension into a microwave reactor for microwave heating treatment, setting the microwave power to be 500W, the heating temperature to be 70 ℃, the stirring speed to be 400r/min and the reaction time to be 70min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device, continuously washing with 50 ℃ high-temperature deionized water for 40min, and after the washing is finished, placing the precipitate into a blast drying oven for drying for 10h.
10g of precipitate and 5% CaO were weighed into a beaker according to 1:7, adding deionized water into the reactor according to the solid-liquid ratio, uniformly mixing the mixture, adding the mixture into a three-phase reactor, and then introducing CO 2 And (3) 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, and the stirring speed to be 600r/min and CO 2 The flow rate was 250mL/min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device again for suction filtration treatment, and adopting the same parameters for the two water washing treatments before and after. After the water washing is finished, the obtained precipitate is dried in a forced air drying oven for 10 hours again. And (3) placing the dried secondary precipitate in a muffle furnace, and calcining at a high temperature of 400 ℃ for 300min to obtain the Fenton iron mud denitration catalyst A.
Example 2
And (3) carrying out dehydration treatment on the original Fenton iron mud with the water content of 95-97%, and carrying out crushing and screening treatment on the dehydrated Fenton iron mud to obtain Fenton iron mud powder.
Taking 20g of pretreated Fenton iron mud powder, placing the powder into a muffle furnace, calcining at 450 ℃ for 60min, cooling to room temperature, and then carrying out the steps of 1:7 solid-to-liquid ratio adding deionized water at 40 ℃ into the Fenton iron mud denitration catalyst precursor. And then placing the suspension into 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 70min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device, continuously washing with 30 ℃ high-temperature deionized water for 45min, and after the washing is finished, placing the precipitate into a blast drying oven for drying for 10h.
10g of precipitate and 6% CaO were weighed into a beaker according to 1:7, adding deionized water into the reactor in a solid-liquid ratio, uniformly mixing the mixture, adding the mixture into a three-phase reactor, and then 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 CO2 flow is 200mL/min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device again for suction filtration treatment, and adopting the same parameters for the two water washing treatments before and after. After the water washing is finished, the obtained precipitate is dried in a forced air drying oven for 10 hours again. And (3) placing the dried secondary precipitate in a muffle furnace, and calcining at a high temperature of 450 ℃ for 330min to obtain the Fenton iron mud denitration catalyst B.
Example 3
And (3) carrying out dehydration treatment on the original Fenton iron mud with the water content of 95-97%, and carrying out crushing and screening treatment on the dehydrated Fenton iron mud to obtain Fenton iron mud powder.
Taking 20g of pretreated Fenton iron mud powder, placing the powder into a muffle furnace, calcining at 450 ℃ for 60min, cooling to room temperature, and then carrying out the steps of 1:8 solid-to-liquid ratio adding 70 ℃ deionized water into the Fenton iron mud denitration catalyst precursor. And then placing the suspension into 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 70min. 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 40 ℃ for 50min, and after the washing is finished, placing the precipitate into a blast drying oven for drying for 10h.
10g of precipitate and 6% CaO were weighed into a beaker according to 1:7, adding deionized water into the reactor in a solid-liquid ratio, uniformly mixing the mixture, adding the mixture into a three-phase reactor, and then 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 CO2 flow is 250mL/min. And after the reaction is finished, adding the suspension into a constant-temperature suction filtration device again for suction filtration treatment, and adopting the same parameters for the two water washing treatments before and after. After the water washing is finished, the obtained precipitate is dried in a forced air drying oven for 12 hours again. And (3) placing the dried secondary precipitate in a muffle furnace, and calcining at a high temperature of 450 ℃ for 300min to obtain the Fenton iron mud denitration catalyst C.
The iron mud catalysts a-C of examples 1 to 3 were selected for denitration efficiency testing and dealkalization rate calculation, and from the test and analysis data (as shown in table 1 and fig. 2): the combined deep dealkalization treatment can lead the dealkalization rate of Fenton iron mud to be more than 80 percent and can reach 87 percent at most; the Fenton iron mud catalyst prepared shows good catalytic activity, and the denitration efficiency can reach more than 90% in the reaction temperature range of 315-430 ℃.
TABLE 1 alkaline substance removal rate Table in Fenton iron mud by combined dealkalization
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (17)
1. A method for preparing a denitration catalyst by Fenton iron mud, which is characterized by comprising the following steps:
(1) Iron mud pretreatment
Carrying out dehydration treatment on the original Fenton iron mud, and carrying out crushing and screening treatment on the dehydrated Fenton iron mud to obtain Fenton iron mud powder;
(2) Primary calcination
Placing the pretreated Fenton iron mud powder into a muffle furnace for high-temperature calcination treatment to obtain a Fenton iron mud denitration catalyst precursor; the high-temperature calcination temperature is 350-500 ℃, and the high-temperature calcination time is 30-120min;
(3) Eluting alkali with high temperature water
After 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, water washing and drying on the suspension to obtain a precipitate;
(4) Deep combined dealkalization
Mixing precipitate, caO and deionized water, adding into a three-phase reactor, and introducing CO 2 The gas, raise reaction temperature and reaction pressure, and regulate the stirring rate; after the reaction is finished, carrying out suction filtration, washing and drying to obtain a secondary precipitate; the content of CaO added is 3% -8% based on the total mass of the precipitate; the pressure in the three-phase reactor is 3-7MPa; the reaction temperature is 60-90 ℃; the reaction time is 60-120min; the stirring speed is 500-1200r/min;CO 2 the flow is 100-300mL/min;
(5) Secondary calcination
Placing the secondary precipitate in a muffle furnace for high-temperature calcination treatment again to obtain the Fenton iron mud denitration catalyst; the high-temperature calcination temperature in the step (5) and the step (2) is the same, and the secondary calcination time is 240-360min.
2. The method of claim 1, wherein the raw Fenton iron sludge has a water content of 95-97%.
3. The method according to claim 1, wherein the high temperature calcination temperature in the step (2) is 400 to 450 ℃ and the high temperature calcination time is 50 to 90min.
4. The method according to claim 1, wherein the suspension in step (3) has a solid-to-liquid ratio of 1:4-12.
5. The method according to claim 4, wherein the suspension in step (3) has a solid-to-liquid ratio of 1:7-9.
6. The method according to claim 1, wherein CaO is added in an amount of 5% -6% based on the total mass of the precipitate in step (4).
7. 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 continuously washed with deionized water at a high temperature of 70-90 ℃, and the obtained precipitate is dried in a blast drying oven for 10-12h after the water washing is finished.
8. The method according to claim 1, wherein in the step (3), the suspension is placed in a microwave reactor for microwave heating treatment, and the microwave power in the microwave reactor is 300-600W; the heating temperature is 40-80 ℃; the stirring speed is 200-800r/min; the reaction time is 30-90min.
9. The method of claim 8, wherein the microwave power in the microwave reactor in step (3) is 400-500W; the heating temperature is 55-65 ℃; the stirring speed is 400-600r/min; the reaction time is 60-80min.
10. The method according to claim 1, wherein the pressure in the three-phase reactor in step (4) is 5 to 6MPa; the reaction temperature is 70-80 ℃; the reaction time is 80-100min; the stirring speed is 600-800r/min; CO 2 The flow rate is 200-250mL/min.
11. The method according to claim 1, wherein the washing time in the step (3) is 20 to 90min; the water washing temperature is 20-60 ℃; the stirring speed is 50-400r/min.
12. The method of claim 11, wherein the washing time in step (3) is 40-60min; the water washing temperature is 30-50 ℃; the stirring speed is 100-200r/min.
13. The method according to claim 7, 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, and the high temperature deionized water is adopted for full continuous water washing treatment, and after the reaction is finished, the obtained precipitate is dried for 10-12 hours in a blast drying box again.
14. The method of claim 1, wherein the secondary calcination time in step (5) is 300 to 330 minutes.
15. The method according to claim 7 or 13, wherein the continuous water washing temperature and time in step (3) and step (4) are the same.
16. Fenton iron mud denitration catalyst prepared by the method according to any one of claims 1-15.
17. The use of the Fenton iron mud denitration catalyst according to claim 16 in the field of flue gas denitration;
the reaction temperature window of the Fenton iron mud denitration catalyst is 300-450 ℃, and the denitration efficiency exceeds 90% in the temperature window.
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| CN114573199A (en) * | 2022-03-17 | 2022-06-03 | 山东省科学院能源研究所 | Fenton iron mud dealkalization and carbon dioxide capture cooperative treatment system and method |
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| CN114573199A (en) * | 2022-03-17 | 2022-06-03 | 山东省科学院能源研究所 | Fenton iron mud dealkalization and carbon dioxide capture cooperative treatment system and method |
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