CN114515576A - Self-supported catalyst and preparation method and application thereof - Google Patents
Self-supported catalyst and preparation method and application thereof Download PDFInfo
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- CN114515576A CN114515576A CN202210222239.8A CN202210222239A CN114515576A CN 114515576 A CN114515576 A CN 114515576A CN 202210222239 A CN202210222239 A CN 202210222239A CN 114515576 A CN114515576 A CN 114515576A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 79
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 239000004202 carbamide Substances 0.000 claims description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 17
- 238000011068 loading method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000000243 solution Substances 0.000 description 25
- 239000011259 mixed solution Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000012495 reaction gas Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005949 ozonolysis reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/106—Ozone
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention relates to a self-supported catalyst, a preparation method and application thereof. The self-supported catalyst comprises foamed iron and nickel-iron layered double hydroxide supported on the foamed iron. The catalyst of the invention has simple preparation process, can stably and efficiently decompose ozone under harsher conditions, and can be applied to the treatment of various gases containing ozone.
Description
Technical Field
The invention belongs to the technical field of environmental catalysis, and relates to a self-supported catalyst, and a preparation method and application thereof.
Background
Ozone is a strong oxidizing gas, and researches show that long-term ozone contact can cause respiratory system diseases, skin aging and even harm human mental health. In the atmosphere, ozone is mainly derived from VOCs and NOxLeading to air quality deterioration. Outdoor ozone can increase indoor ozone concentration through air exchange. The use of air purifiers and copiers also increases the indoor ozone concentration. On the other hand, due to the ozone in the disinfection field and the high grade of waste gases and waste water For wide-spread use in oxidation treatment, ozone in the exhaust gas also needs to be removed before being released into the air. Therefore, the elimination of ozone is of great importance for the protection of humans and the environment.
Currently, catalytic decomposition is considered the best method for eliminating ozone. CN111408378A discloses a powdered catalyst for ozonolysis, which is a layered double hydroxide possessing a nickel-iron hydrotalcite structure, having excellent ozonolysis activity and stability. However, in practice, the powder catalyst must be impregnated or coated on a honeycomb ceramic or other support. The coating process of the powder catalyst is complex, the binding force between the catalyst and the carrier is weak, and the performance of the whole catalyst is easy to deteriorate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a self-loading catalyst which has a simple preparation process, can stably and efficiently decompose ozone under harsher conditions and can be applied to the treatment of various gases containing ozone.
A first aspect of the invention provides a self-supported catalyst comprising foamed iron and a layered double hydroxide of nickel iron supported on the foamed iron. In the invention, the foam iron not only serves as a self-supporting carrier to bear the ferronickel layered double hydroxide, but also can play a role of a certain active component to promote the catalytic decomposition of ozone.
According to some embodiments of the invention, the iron element in the nickel iron layered double hydroxide is derived from foamed iron. The firmness between the catalyst and the carrier has important influence on the service life of the whole catalyst, and the invention ingeniously adopts the foamed iron to provide the iron element used in the synthesis of the layered nickel-iron bimetal hydroxide, thereby greatly improving the binding force between the layered nickel-iron bimetal hydroxide and the foamed iron and improving the structural stability of the catalyst.
According to some embodiments of the present invention, the loading amount of the nickel-iron layered double hydroxide is (10-40 mg)/cm based on the mass of nickel element3. In some embodiments, the loading of the nickel iron layered double hydroxideThe amount is 11mg/cm3、13mg/cm3、15mg/cm3、16mg/cm3、17mg/cm3、18mg/cm3、19mg/cm3、20mg/cm3、21mg/cm3、23mg/cm3、25mg/cm3、27mg/cm3、29mg/cm3、30mg/cm3、32mg/cm3、34mg/cm3、36mg/cm3、38mg/cm3Or any value therebetween. In some embodiments, the loading of the nickel iron layered double hydroxide is (14mg-20mg)/cm3。
The second aspect of the present invention provides a method for preparing a self-supported catalyst, which comprises mixing foamed iron with a first solution comprising a nickel source and a precipitant, and then performing a hydrothermal reaction.
According to some embodiments of the invention, the method further comprises washing the resulting self-supported catalyst to neutral and dry after completion of the hydrothermal reaction. In some embodiments, the temperature of the drying is 60 ℃ to 90 ℃ and the time of the drying is 4h to 12 h.
According to the invention, the foamed iron is used as a self-loading carrier, and the nickel-iron layered double hydroxide/foamed iron monolithic catalyst is successfully synthesized by adopting a simple one-step hydrothermal method, wherein the foamed iron is used as a carrier and an iron source for synthesizing the nickel-iron layered double hydroxide, so that the binding force between the nickel-iron layered double hydroxide and the foamed iron can be greatly improved, and the catalytic performance and the structural stability of the catalyst are improved.
According to some embodiments of the invention, the molar ratio of the nickel source to the precipitant, calculated as nickel element, in the first solution is 1 (1-15), such as 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or any value in between. In some embodiments, the molar ratio of the nickel source to the precipitant is 1 (1-10). In some embodiments, the molar ratio of the nickel source to the precipitant is 1 (2.5-5).
According to some embodiments of the invention, the concentration of the nickel source in the first solution is between 0.03mmol/mL and 0.1 mmol/mL. In some embodiments, the concentration of the nickel source is 0.035mmol/mL, 0.04mmol/mL, 0.045mmol/mL, 0.05mmol/mL, 0.055mmol/mL, 0.06mmol/mL, 0.065mmol/mL, 0.07mmol/mL, 0.075mmol/mL, 0.08mmol/mL, 0.085mmol/mL, 0.09mmol/mL, 0.095mmol/mL, or any value therebetween.
According to some embodiments of the invention, the concentration of the precipitating agent in the first solution is between 0.05mmol/mL and 0.5 mmol/mL. In some embodiments, the precipitant has a concentration of 0.07mmol/mL, 0.04mmol/mL, 0.09mmol/mL, 0.1mmol/mL, 0.13mmol/mL, 0.15mmol/mL, 0.17mmol/mL, 0.19mmol/mL, 0.20mmol/mL, 0.23mmol/mL, 0.25mmol/mL, 0.27mmol/mL, 0.29mmol/mL, 0.30mmol/mL, 0.33mmol/mL, 0.35mmol/mL, 0.37mmol/mL, 0.39mmol/mL, 0.40mmol/mL, 0.43mmol/mL, 0.45mmol/mL, 0.47mmol/mL, 0.49mmol/mL, or any value therebetween.
According to some embodiments of the invention, the volume ratio of the foamed iron to the first solution is 1 (10-40). In some embodiments, the volume ratio of the foamed iron to the first solution is 1:10, 1:11, 1:13, 1:15, 1:17, 1:19, 1:20, 1:21, 1:23, 1:25, 1:27, 1:29, 1:30, 1:31, 1:33, 1:35, 1:37, 1:39, or any value therebetween.
According to some embodiments of the invention, the temperature of the hydrothermal reaction is 90 ℃ to 150 ℃, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 35 ℃, 140 ℃ or 145 ℃. In some embodiments, the hydrothermal reaction is for a time of 4h to 12h, e.g., 5h, 6h, 7h, 8h, 9h, 10h, or 11 h.
According to some embodiments of the invention, the nickel source is selected from one or more of soluble nickel salts. In some embodiments, the nickel source is selected from one or more of nickel nitrate, nickel chloride, and nickel sulfate.
According to some embodiments of the invention, the precipitating agent is selected from urea.
According to some embodiments of the invention, the first solution comprises a nickel source, a precipitating agent, and water. In some embodiments, the first solution consists of a nickel source, a precipitating agent, and water.
According to some embodiments of the invention, the method for preparing the self-supported catalyst comprises the following specific steps: dissolving a nickel source and a precipitator in water, stirring to uniformly mix the solution, adding the solution into a hydrothermal reaction kettle, adding a piece of iron foam into the reaction kettle, sealing and placing the reaction kettle in an oven at the temperature of 90-150 ℃ for reaction for 4-12 h, after the reaction is finished, cooling the hydrothermal reaction kettle to room temperature, washing the obtained catalyst to be neutral, and drying to obtain the self-supported catalyst.
The third aspect of the present invention provides the use of the self-supported catalyst of the first aspect or the self-supported catalyst obtained by the preparation method of the second aspect for catalytically decomposing ozone.
According to some embodiments of the invention, the self-supported catalyst is used for catalytically decomposing an ozone-containing gas. In some embodiments, the self-supported catalyst is used for catalytic decomposition of ozone in air. In some embodiments, the self-supported catalyst is used for removing ozone from the atmosphere on exterior surfaces of buildings and in automotive radiators. In some embodiments, the self-supported catalyst is used in indoor and high altitude aircraft to remove ozone in enclosed spaces. In some embodiments, the self-supported catalyst is used for the removal of ozone from water-treated exhaust gas.
In a fourth aspect of the present invention, there is provided a method for treating an ozone-containing gas, comprising contacting an ozone-containing gas with a catalyst and then reacting the ozone-containing gas with the catalyst, wherein the catalyst is the self-supported catalyst according to the first aspect or the self-supported catalyst obtained by the preparation method according to the second aspect.
According to some embodiments of the present invention, the ozone-containing gas has a relative humidity RH ≧ 40%, such as 45%, 50%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any value therebetween. In some embodiments, the ozone-containing gas has a relative humidity RH ≧ 60%.
According to some embodiments of the invention, the ozone-containing gas has a concentration of ozone greater than 0.1 ppm. In some embodiments, the ozone-containing gas has an ozone concentration of 1ppm, 5ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 70ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, or any value therebetween.
According to some embodiments of the invention, the ozone-containing gas has a space velocity of 50000h-1-150000h-1E.g. 60000h-1、70000h-1、80000h-1、90000h-1、100000h-1、110000h-1、120000h-1、130000h-1、140000h-1Or any value therebetween.
According to some embodiments of the invention, the reaction temperature is 5 ℃ to 40 ℃, such as 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃. In some embodiments, the reaction temperature is ambient temperature.
The invention successfully synthesizes the ferronickel layered double hydroxide/foamed iron monolithic catalyst by a simple one-step hydrothermal method, and when the catalyst is applied to ozonolysis, the relative humidity is 65 percent and the reaction time is 102314h-1The catalyst has excellent ozone conversion rate and stability at the air hourly space velocity, and has high application value and practicability.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention successfully synthesizes the ferronickel layered double hydroxide/foamed iron monolithic catalyst by a simple one-step hydrothermal method, and when the catalyst is applied to ozonolysis, the relative humidity is 65 percent and the reaction time is 102314h -1The catalyst has excellent ozone conversion rate and stability at the air hourly space velocity, and has high application value and practicability.
(2) The self-supported catalyst is applied to catalytic decomposition of ozone, and the conversion rate of the prepared catalyst for catalyzing ozone can reach 92.8% by adjusting the addition amounts of the precipitator and the iron source in the preparation process of the self-supported catalyst.
Drawings
Figure 1 is the XRD pattern of the self-supported catalyst described in example 9.
FIG. 2 is an SEM image of a self-supported catalyst of example 9.
Fig. 3 is an SEM image of the foamed iron.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
0.5, 1, 1.5, 2, 2.5 and 3mmol of nickel nitrate hexahydrate (Ni (NO) are weighed3)2·6H2Dissolving O) and 1, 2, 3, 4, 5, 6, 10, 15 and 20mmol of Urea (Urea) in 20-40mL (natural number between 20 and 40) of deionized water, stirring for 20min to uniformly mix the solution, adding the solution into a 50mL hydrothermal reaction kettle, adding a piece of 2mm multiplied by 20mm multiplied by 30mm iron foam into the reaction kettle, sealing and placing the reaction kettle in an oven at 90-150 ℃ for 4h-12h, after the reaction is finished, cooling the hydrothermal kettle to room temperature, washing the obtained monolithic catalyst to be neutral, and drying the monolithic catalyst (60-90 ℃ for 5h-15h) to obtain a blocky self-supported catalyst which is named as IF-a-b-c, wherein a is 0.5, 1, 1.5, 2, 2.5 and 3 and represents nickel nitrate hexahydrate (Ni (NO) (NO is a natural number of 0.5, 1, 1.5, 2, 2.5 and 3) 3)2·6H2O) the amount used. b is 1, 2, 3, 4, 5, 10, 15, 20 and represents the dosage of urea. c is 20-40 (natural number between 20 and 40), and represents the water consumption.
An SEM image of the iron foam used in the examples of the present invention is shown in fig. 3.
Example 1
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 1mmol of Urea (Urea) are dissolved in 20mL of deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-1-20.
Example 2
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 2mmol Urea (Urea) are dissolved in 20mL deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) Adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-2-20.
Example 3
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 3mmol Urea (Urea) are dissolved in 20mL deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-3-20.
Example 4
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 4mmol Urea (Urea) are dissolved in 20mL deionized water and stirred for 20min to ensure that the solution is uniformly mixed to obtain a mixtureMixing the solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-4-20.
Example 5
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 5mmol Urea (Urea) are dissolved in 20mL deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-5-20.
Example 6
This example provides a self-supported catalyst, which is prepared as follows:
(1) 1mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 6mmol Urea (Urea) are dissolved in 20mL deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-1-6-20.
Example 7
This example provides a self-supported catalyst, which is prepared as follows:
(1) weighing 2mmol nickel nitrate hexahydrate (Ni (NO)3)2·6H2O) and 10mmol of Urea (Urea) are dissolved in 40mL of deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-2-10-40.
Example 8
This example provides a self-supported catalyst, which is prepared as follows:
(1) 2.5mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 10mmol of Urea (Urea) are dissolved in 40mL of deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-2.5-10-40.
Example 9
This example provides a self-supported catalyst, which is prepared as follows:
(1) 3mmol of nickel nitrate hexahydrate (Ni (NO) was weighed3)2·6H2O) and 10mmol of Urea (Urea) are dissolved in 40mL of deionized water and stirred for 20min, so that the solution is uniformly mixed to obtain a mixed solution;
(2) adding the mixed solution into a 50mL hydrothermal reaction kettle, adding a piece of 2X 20X 30mm iron foam into the reaction kettle, sealing and placing the mixture in a 120 ℃ oven for reaction for 6h, cooling the hydrothermal kettle to room temperature after the reaction is finished, washing the obtained monolithic catalyst to be neutral, and drying (60 ℃, 10h) to obtain the blocky monolithic self-supported catalyst IF-3-10-40.
The XRD pattern of the self-supported catalyst IF-3-10-40 is shown in figure 1, and the SEM pattern of the self-supported catalyst IF-3-10-40 is shown in figure 2.
Comparative example 1
This comparative example provides a self-supported catalyst prepared as follows:
adding 1g of NiFe-LDH catalyst, 20mL of deionized water and 3g of alumina sol into a beaker, magnetically stirring for 20min, uniformly mixing, soaking a cordierite carrier with the diameter of 8mm and the thickness of 14mm in the obtained mixed solution for 1s, taking out, blowing off the redundant solution in a pore channel by using an aurilave, drying in an oven at 60 ℃, and repeatedly soaking until the loading capacity of the catalyst reaches more than 30 mg.
Comparative example 2
This comparative example provides a self-supported catalyst prepared as follows:
firstly, cutting the aluminum foam with the thickness of 2mm into 7 round pieces with the diameter of 8mm for standby. Adding 1g of NiFe-LDH catalyst, 20mL of deionized water and 3g of alumina sol into a beaker, magnetically stirring for 20min, uniformly mixing, sequentially soaking 7 aluminum foam wafer carriers with the diameter of 8mm in the obtained mixed solution for 1s respectively, taking out, blowing off the redundant solution in a pore channel by using an ear washing ball, drying in a 60 ℃ oven, and repeatedly soaking until the total catalyst load (load on 7 aluminum foam wafers) reaches more than 30 mg.
And (4) performance testing:
(1) the self-supported catalysts prepared in examples 1 to 9 were each cut into a circular piece having a diameter of 8mm for use. 7 pieces of the monolithic catalyst having a thickness of 2mm and a diameter of 8mm were charged into a quartz glass tube having a diameter of 8mm, and then a reaction gas (ozone-containing air) was introduced. Wherein the total gas flow is 1.2L/min, and the ozone concentration is 20ppm (C)in20ppm), test temperature T30 ℃, reaction gas humidity RH 65%, GHSV 102,314h-1The test time is 6h, and the specific test result is shown inTable 1;
the catalyst prepared in comparative example 1 was charged in a quartz glass tube having a diameter of 8mm, and then a reaction gas (ozone-containing air) was introduced. Wherein the total gas flow is 1.2L/min, and the ozone concentration is 20ppm (C)in20ppm), test temperature T30 ℃, reaction gas humidity RH 65%, GHSV 102,314h-1The testing time is 6h, and the specific testing result is shown in table 1;
7 pieces of the catalyst prepared in comparative example 2 having a thickness of 2mm and a diameter of 8mm were charged into a quartz glass tube having a diameter of 8mm, and then a reaction gas (ozone-containing air) was introduced. Wherein the total gas flow is 1.2L, and the ozone concentration is 20ppm (C)in20ppm), test temperature T30 ℃, reaction gas humidity RH 65%, GHSV 102,314h -1The test time is 6h, and the specific test result is shown in table 1;
the monolithic catalysts prepared in example 3 were each cut into disks having a diameter of 8 mm. 7 pieces of the monolithic catalyst having a thickness of 2mm and a diameter of 8mm were charged into a quartz glass tube having a diameter of 8mm, and then a reaction gas (ozone-containing air) was introduced. Wherein the total gas flow is 1.2L/min, and the ozone concentration is 20ppm (C)in20ppm), test temperature T30 ℃, reaction gas humidity RH 65%, GHSV 102,314h-1The test time is 168h, (O)3Conversion rate ═ Cin-Cout)/CinX 100%, wherein CinConcentration of ozone in the reaction gas before reaction, CoutIs the concentration of ozone in the reaction gas after the reaction. ) The specific test results are shown in table 1.
TABLE 1
As can be seen from Table 1, from the ozonolysis activities of examples 1 to 6, the activity of the catalyst increased first and then decreased with the increase of the amount of urea, the activity of the catalyst was optimal when the amount of urea added was 3mmol (example 3), the ozone removal rate of 91.5% was achieved within 6 hours, and the ozone removal rate of 85% was maintained after 168 hours in example 3, showing good stability.
From examples 7-9, it can be seen that the activity of the catalyst is dependent on Ni2+The amount of the additive increases.
Comparative examples 1 and 2 deactivated after 0.5 hours and 2 hours respectively, indicating that this example of nickel iron layered double hydroxide self-supported with foamed iron performs better in ozonolysis reactions than the comparative example prepared by late-loading the nickel iron layered double hydroxide by impregnation.
(2) Firmness test between catalyst and support: three pieces of catalyst IF-1-3-20 prepared in example 3 were put in an ultrasonic apparatus, and subjected to ultrasonic treatment for 10min, respectively, and the quality of IF-1-3-20 before and after ultrasonic treatment was recorded, and the test results are shown in Table 2:
TABLE 2
As can be seen from Table 2, the catalyst of the present invention has a stable structure and can still ensure the ozone conversion rate after ultrasonic treatment.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A self-supported catalyst comprising a foamed iron and a layered double hydroxide of nickel-iron supported on the foamed iron.
2. The self-supported catalyst of claim 1, wherein the iron element of the nickel iron layered double hydroxide is derived from foamed iron.
3. Self-supported catalyst according to claim 1 or 2, characterized in thatThe loading capacity of the nickel-iron layered double hydroxide is 10-40 mg/cm based on the mass of nickel element3。
4. A preparation method of a self-supported catalyst is characterized by comprising the steps of mixing foamed iron with a first solution containing a nickel source and a precipitator, and then carrying out hydrothermal reaction.
5. The preparation method according to claim 4, wherein the molar ratio of the nickel source to the precipitant in the first solution is 1 (1-15), preferably 1 (1-10), and more preferably 1 (2.5-5) in terms of nickel element;
preferably, in the first solution, the concentration of the nickel source is 0.03-0.1 mmol/mL;
preferably, the concentration of the precipitator is 0.05-0.5 mmol/mL;
preferably, the volume ratio of the foam iron to the first solution is 1 (10-40).
6. The preparation method according to claim 4 or 5, wherein the temperature of the hydrothermal reaction is 90-150 ℃;
Preferably, the hydrothermal reaction time is 4-12 h.
7. The method according to any one of claims 4 to 7, wherein the nickel source is selected from one or more of soluble nickel salts, preferably from one or more of nickel nitrate, nickel chloride and nickel sulfate;
preferably, the precipitating agent is selected from urea;
preferably, the first solution comprises, preferably consists of, a nickel source, a precipitating agent and water.
8. Use of a self-supported catalyst according to any one of claims 1 to 3 or obtained by the preparation process according to any one of claims 4 to 7 for the catalytic decomposition of ozone, preferably for the catalytic decomposition of ozone-containing gas.
9. A method for treating an ozone-containing gas, which comprises bringing an ozone-containing gas into contact with a catalyst and then reacting the ozone-containing gas with the catalyst, wherein the catalyst is the self-supported catalyst according to any one of claims 1 to 3 or the self-supported catalyst obtained by the production method according to any one of claims 4 to 7.
10. The method according to claim 9, wherein the ozone containing gas has a relative humidity RH > 40%, preferably RH > 60%;
And/or the concentration of ozone in the ozone containing gas is greater than 0.1 ppm;
and/or the space velocity of the ozone-containing gas is 50000-150000 h-1。
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