CN114515576A - Self-supported catalyst and preparation method and application thereof - Google Patents

Self-supported catalyst and preparation method and application thereof Download PDF

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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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nickel
ozone
self
iron
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CN114515576B (en
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贺泓
马金珠
王志胜
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Research Center for Eco Environmental Sciences of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8671Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B01D53/8675Ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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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

Self-supported catalyst and preparation method and application thereof
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
Figure BDA0003537942700000121
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
Figure BDA0003537942700000131
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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