CN111495410A - Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof - Google Patents
Honeycomb ceramic-porous carbon monolithic catalyst, honeycomb ceramic-porous carbon monolithic adsorbent and preparation method and application thereof Download PDFInfo
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- CN111495410A CN111495410A CN202010354196.XA CN202010354196A CN111495410A CN 111495410 A CN111495410 A CN 111495410A CN 202010354196 A CN202010354196 A CN 202010354196A CN 111495410 A CN111495410 A CN 111495410A
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- honeycomb ceramic
- porous carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 129
- 239000003463 adsorbent Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 131
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 119
- 150000001412 amines Chemical class 0.000 claims abstract description 63
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- 238000006243 chemical reaction Methods 0.000 claims description 88
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 72
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
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- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 50
- 229910052878 cordierite Inorganic materials 0.000 claims description 41
- 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 claims description 41
- TVCXVUHHCUYLGX-UHFFFAOYSA-N 2-Methylpyrrole Chemical compound CC1=CC=CN1 TVCXVUHHCUYLGX-UHFFFAOYSA-N 0.000 claims description 35
- FEKWWZCCJDUWLY-UHFFFAOYSA-N 3-methyl-1h-pyrrole Chemical compound CC=1C=CNC=1 FEKWWZCCJDUWLY-UHFFFAOYSA-N 0.000 claims description 35
- 229920002873 Polyethylenimine Polymers 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 34
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 34
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 34
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
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- B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
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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
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a honeycomb ceramic-porous carbon integral catalyst, a honeycomb ceramic-porous carbon integral adsorbent and a preparation method and application thereof. The honeycomb ceramic-porous carbon integral adsorbent consists of a honeycomb ceramic-porous carbon composite material carrier and organic amine, and organic amine is loaded on the honeycomb ceramic-porous carbon composite material carrier through an impregnation method to obtain the honeycomb ceramic-porous carbon-organic amine integral adsorbent which can show good carbon dioxide adsorption performance.
Description
Technical Field
The invention relates to a honeycomb ceramic-porous carbon integral composite material, in particular to a honeycomb ceramic-porous carbon integral catalyst, a honeycomb ceramic-porous carbon integral adsorbent, a preparation method and an application thereof.
Background
Since the industrial revolution, the concentration of carbon dioxide in the atmosphere has been continuously increased due to the massive use of fossil fuels, exceeding 415ppm in 2019, which makes the global warming phenomenon caused by the greenhouse effect to be increasingly serious. At present, people mainly utilize organic amine solution to capture CO generated by petroleum combustion2The gas, organic amine used includes ethanolamine (MEA), Diethanolamine (DEA), Tetraethylenepentamine (TEPA) and the like. Although organic amine solution is used to capture CO2The method is very effective, but the organic amine has poor chemical stability, low gas transmission efficiency, large regeneration energy consumption and strong corrosion to instruments. Therefore, it is necessary and urgent to develop a new carbon dioxide separation and capture technology to reduce carbon dioxide emissions and to alleviate climate warming.
In addition, there is a certain amount of ozone in the atmosphere. The limit concentration of ozone acceptable by ordinary people in one hour is 260ug/m3At 320ug/m3Cough, dyspnea and decreased lung function occur after 1 hour of activity in an ozone environment. Ozone can also participate in the reaction of unsaturated fatty acid, amino and other proteins in organisms, so that people who directly contact ozone for a long time have symptoms of fatigue, cough, chest distress and pain, skin wrinkling, nausea and headache, accelerated pulse, memory deterioration, visual deterioration and the like. Therefore, the development of a new catalytic ozonolysis technology, reducing ozone in the environment, is a constant goal of researchers.
Xiaochun Xu et al (Energy & Fuels, 2002, 16, 1463-. However, the adsorbent is in powder form, and thus it is difficult to industrially apply the adsorbent in large quantities, mainly because the use of a large amount of powder material may clog piping equipment, resulting in a pressure drop before and after the adsorbent.
Chinese patent CN103495409B discloses a method for preparing the carbon-honeycomb ceramic monolithic catalyst, which comprises immersing cordierite honeycomb ceramic subjected to acidification treatment in resin in advance, taking out the cordierite honeycomb ceramic, blowing off redundant resin, heating to 50-200 ℃ for curing treatment, and finally carbonizing at 400-600 ℃ in an argon atmosphere. However, the carbon-honeycomb ceramic monolithic catalyst prepared by the method is easily blocked due to the need of being impregnated in resin. Chinese patent CN202700366U discloses a ceramic honeycomb activated carbon body with mechanical control mechanical holes prepared by sintering ceramic slurry and activated carbon at high temperature. According to the method, the ceramic slurry and the activated carbon are sintered at high temperature, so that the integral composite material is brittle in structure and easy to break, and the stability of the integral composite material is greatly reduced.
In summary, the problems of decomposition of ozone and adsorption of carbon dioxide in the prior art need to be further studied and discussed to develop a material capable of effectively decomposing ozone and adsorbing carbon dioxide, optimize the preparation process of the material, and improve the material performance, so that the material has better application effect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a honeycomb ceramic-porous carbon monolithic catalyst, a honeycomb ceramic-porous carbon monolithic adsorbent and a preparation method thereof.
In order to achieve the purpose, the technical scheme is that the honeycomb ceramic-porous carbon monolithic catalyst is a honeycomb ceramic-porous carbon monolithic composite material, the monolithic catalyst is composed of a carrier and an active component, the content of the active component is 1-15 wt% of the total mass of the monolithic catalyst, the carrier is monolithic honeycomb ceramic, and the active component is nitrogen-phosphorus-doped porous carbon.
In one embodiment of the invention, the active component is loaded by a chemical gas phase polymerization and high-temperature carbonization activation method, and the carrier is monolithic cordierite honeycomb ceramic.
A preparation method of a honeycomb ceramic-porous carbon monolithic catalyst comprises the following steps:
step 1, loading phosphoric acid and/or pyrophosphoric acid on the surface of integral honeycomb ceramic by an impregnation method, drying, and generating a layer of polypyrrole compound on the surface of integral honeycomb ceramic by a chemical vapor polymerization method at 140-220 ℃ in a reaction kettle;
2, loading phosphoric acid and/or pyrophosphoric acid by an impregnation method again;
and 3, converting the polypyrrole compound into a porous carbon material by a high-temperature carbonization activation method, wherein the high-temperature carbonization activation temperature is 500-1000 ℃, and the high-temperature carbonization activation time is 1-3 hours, so that the honeycomb ceramic-porous carbon integral catalyst is obtained.
Wherein, in the step 1, when phosphoric acid and pyrophosphoric acid are added as polymerization agents at the same time, the molar ratio of the mixture of phosphoric acid and pyrophosphoric acid added is (1-5) to (0.5-5); in the step 2, if phosphoric acid and pyrophosphoric acid are added as activating agents at the same time, the molar ratio of the phosphoric acid to the pyrophosphoric acid is (1-5) to (0.5-5).
In an embodiment of the present invention, the precursor of the polypyrrole-based compound is any one of pyrrole, 2-methylpyrrole, and 3-methylpyrrole, or a mixture of any two or more of them. When the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed, the mass ratio of the pyrrole to the 2-methylpyrrole to the 3-methylpyrrole is (0.5-5) to (0.5-5).
In one embodiment of the present invention, the monolithic honeycomb ceramic is a monolithic cordierite honeycomb ceramic.
And soaking the cordierite honeycomb ceramic into a mixed solution of phosphoric acid and pyrosulfuric acid with a certain concentration, taking out the cordierite honeycomb ceramic, and drying the cordierite honeycomb ceramic to remove water to obtain the honeycomb ceramic material with phosphoric acid and pyrophosphoric acid loaded on the surface. Placing the honeycomb ceramic material with the surface loaded with the phosphoric acid and the pyrophosphoric acid in a reaction kettle, placing a small bottle in the reaction kettle, adding a mixture of pyrrole, 2-methylpyrrole and 3-methylpyrrole in the small bottle, and sealing the reaction kettle. And (3) putting the reaction kettle into an oven at 140-220 ℃ for 8 hours, volatilizing pyrrole, 2-methylpyrrole and 3-methylpyrrole at high temperature to form pyrrole gas, and generating a polymerization reaction after the pyrrole gas meets phosphoric acid and pyrophosphoric acid loaded on the surfaces of the honeycomb ceramic pore channels to generate a polypyrrole compound on the surfaces of the honeycomb ceramic pore channels. Taking the honeycomb ceramic with the polypyrrole compound loaded on the surface out of the reaction kettle, soaking the honeycomb ceramic in the mixed solution of phosphoric acid and pyrosulfuric acid for 5 minutes, taking the honeycomb ceramic out, placing the honeycomb ceramic into a tubular furnace, and carbonizing the honeycomb ceramic in an inert gas atmosphere at 500-plus-one temperature of 1000 ℃ for 1-3 hours to obtain the honeycomb ceramic-porous carbon integral composite material.
The purpose of re-dipping the mixed solution of phosphoric acid and pyrosulfuric acid is to activate the phosphoric acid and the pyrophosphoric acid in the carbonization process, so that a carbon material with high specific surface area can be obtained on the surface of the honeycomb ceramic, and the carbon material is tightly combined with the honeycomb ceramic and is not easy to fall off. The honeycomb ceramic-porous carbon integral composite material is an ozone decomposition catalyst and can be directly applied to ozone catalytic decomposition reaction.
The honeycomb ceramic-porous carbon monolithic catalyst is applied to ozone decomposition.
The honeycomb ceramic-porous carbon integral adsorbent consists of an adsorbent carrier and an adsorbent active component, wherein the adsorbent carrier is a honeycomb ceramic-porous carbon integral composite material, and the adsorbent active component is organic amine
In an embodiment of the present invention, the organic amine is loaded by a co-impregnation method, and the organic amine is any one of or a mixture of any two or more of tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine. When the three are mixed for use, the mass ratio of the tetraethylenepentamine to the pentaethylenehexamine to the polyethyleneimine is (0.1-5) to (0.1-5).
A preparation method of a honeycomb ceramic-porous carbon integral adsorbent comprises the steps of immersing a honeycomb ceramic-porous carbon integral composite material into a methanol mixed solution of tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine in a certain mass ratio, wherein the mass ratio of the tetraethylenepentamine to the pentaethylenehexamine to the polyethyleneimine is (0.1-5): 0.1-5), carrying out ultrasonic treatment, taking out, and removing a solvent in a vacuum drying oven to obtain the honeycomb ceramic-porous carbon-organic amine integral composite material.
The adsorbent of the invention adopts the honeycomb ceramic-porous carbon integral composite material as a carrier, and the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine as the active components of the adsorbent, thereby realizing the carbon dioxide adsorption with low mass transfer resistance.
The honeycomb ceramic-porous carbon monolithic adsorbent is applied to carbon dioxide adsorption.
The technical scheme has the following beneficial effects:
according to the invention, the honeycomb ceramic is used as a carrier, phosphoric acid and pyrophosphoric acid are loaded on the surface of the honeycomb ceramic and used as polymerization reagents of pyrrole compounds, the pyrrole compounds are volatilized in a reaction kettle, pyrrole steam contacts the surface of the honeycomb ceramic to generate chemical gas phase polymerization reaction on the surface of the honeycomb ceramic, the polypyrrole compounds are generated, the phosphoric acid and pyrophosphoric acid are soaked again to be used as chemical activators, and then high-temperature carbonization and activation are carried out under nitrogen gas, so that a layer of porous carbon material doped with nitrogen and phosphorus is successfully generated on the surface of the honeycomb ceramic, namely the honeycomb ceramic-porous carbon integral composite material. The honeycomb ceramic-porous carbon monolithic composite material can be directly used as an ozone catalytic decomposition catalyst, realizes the catalytic decomposition of ozone at normal temperature, and solves the pressure drop problem of a powder catalyst.
The honeycomb ceramic-porous carbon-organic amine monolithic adsorbent is prepared by loading organic amine on the honeycomb ceramic-porous carbon monolithic composite material, so that the carbon dioxide in the mixed gas is completely removed, the carbon emission is reduced, and the problem of pressure drop of the powder adsorbent is solved.
The honeycomb ceramic-porous carbon integral composite material developed by the invention has the characteristics of simple manufacturing process, high activity, good stability and the like, solves the problem of pressure drop in practical application, and can realize the amplification use of a catalyst or an adsorbent.
Drawings
In FIG. 1, a is a honeycomb ceramic raw material, and b is a honeycomb ceramic-porous carbon monolithic composite prepared in example 5;
FIG. 2 shows a SEM photograph of a honeycomb ceramic raw material and b a SEM photograph of a honeycomb ceramic-porous carbon monolithic composite prepared in example 5;
FIG. 3 is a TEM photograph of the honeycomb ceramic-porous carbon monolithic composite prepared in example 5;
in fig. 4, a and b are XPS spectra of the honeycomb ceramic raw material and the honeycomb ceramic-porous carbon monolithic composite prepared in example 5, respectively;
FIG. 5 is a graph comparing the conversion of 1, 2 and 3 honeycomb ceramic-porous carbon monolithic composite catalysts prepared in example 5 to catalytic removal of ozone;
fig. 6 is a graph of carbon dioxide breakthrough at 75 ℃ for 1, 2, and 3 honeycomb ceramic-porous carbon-organic amine monolithic composite adsorbents prepared in example 5.
Detailed Description
The invention will now be further described with reference to the following examples and figures 1 to 6.
Example 1
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 2.00M/L and 0.50M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 1.00g of 2-methylpyrrole and 1.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:1: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 160 ℃ oven for reacting for 8 hours, taking out and then putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 2.00M/L and 0.50M/L), soaking for 30 minutes, taking out and drying, and then obtaining the calcined honeycomb ceramic-porous carbon monolithic composite material with the weight of about 11.00g and weight of 11.00.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.33g of tetraethylenepentamine, 0.33g of pentaethylenehexamine and 0.33g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 1:1: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying oven to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material with the weight of about 12.00g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the performance evaluation of the adsorbent was carried out in a stainless steel reactor having an inner diameter of 22mm and a length of 200mm, and the obtained honeycomb ceramic-porous carbon monolithic composite was directly charged into a tube. The weight of the catalyst is 1 block of honeycomb ceramic-porous carbon monolithic composite material, the weight is about 11.00g, wherein, about 10.00g is honeycomb ceramic, 1.00g is porous carbon, and the porous carbon isAn ozone decomposition catalyst. 2, 3 or more honeycomb ceramic-porous carbon monolithic composites can also be used as the catalyst. The raw material gas comprises the following components (by volume): 22ppm of O3+ air, gas flow rate 1.2L/min, catalytic reaction temperature 25 ℃, catalyst activity is expressed in terms of ozone conversion after 10.5h of continuous operation of the catalyst, and catalytic reaction performance is shown in table 1.
(4) Sorbent performance testing:
the performance evaluation of the adsorbent is carried out in a fixed bed reactor with the inner diameter of 22mm and the length of 200mm, the honeycomb ceramic-porous carbon-organic amine integrated composite material is loaded into the fixed bed reactor, and the carbon dioxide adsorption quantity is tested by a penetration curve method. The adsorbent is 1 honeycomb ceramic-porous carbon-organic amine monolithic composite material, the weight is about 12.00g, wherein about 10.00g is honeycomb ceramic, 1.00g is porous carbon, and 1.00g is organic amine. 2, 3 or more honeycomb ceramic-porous carbon-organic amine monolithic composite materials can also be used as the adsorbent. The raw material gas composition is (raw material gas volume combination): 10% CO2+90％N2The flow rate of the mixed gas is 10 ml/min-1. The adsorption temperature was 75 ℃. The performance of the adsorbent is expressed in terms of the amount of carbon dioxide adsorbed per unit mass of the adsorbent, and the specific algorithm is to divide the amount of carbon dioxide adsorbed by (the sum of the masses of the porous carbon and the organic amine, which is 2.00g in this example), and the honeycomb ceramic is used as a carrier, and the mass thereof is not calculated in the total mass of the adsorbent. The adsorption performance of the adsorbent is shown in table 1.
Example 2
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 3.00M/L and 1.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 1.50g of pyrrole, 1.00g of 2-methylpyrrole and 0.50g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 3:2: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 200 ℃ oven for reacting for 6 hours, taking out and then putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 3.00M/L and 1.00M/L), soaking for 30 minutes, taking out and drying, and then obtaining the calcined honeycomb ceramic-porous carbon monolithic composite material with the weight of about 10.95g and the weight of 10..
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.50g of tetraethylenepentamine, 0.25g of pentaethylenehexamine and 0.25g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:1: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.95g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 3
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 300-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 2.00M/L and 2.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 2.00g of pyrrole, 0.50g of 2-methylpyrrole and 0.50g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 4:1: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into an oven with the temperature of 180 ℃ for reacting for 6 hours, taking out and putting the mixture into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 2.00M/L and 2.00M/L) again for soaking for 30 minutes, taking out and drying, and then obtaining the calcined honeycomb ceramic-porous carbon monolithic composite material with the weight of about 10.80.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.40g of tetraethylenepentamine, 0.30g of pentaethylenehexamine and 0.10g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 4:3: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.60g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 4
(1) Preparing a honeycomb ceramic-porous carbon composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 3.00g of pyrrole, 1.00g of 2-methylpyrrole and 1.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 3:1: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into an oven with the temperature of 180 ℃ for reacting for 6 hours, taking out and putting the mixture into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L) again for soaking for 30 minutes, taking out and drying, and then obtaining the calcined honeycomb ceramic-porous carbon monolithic composite material with the weight of about 11.20.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.40g of tetraethylenepentamine, 0.60g of pentaethylenehexamine and 0.20g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:3: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 12.40g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 5
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g, see figure 1a) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g, see figure 1a) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is 1.00M/L and 5.00M/L respectively), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and then putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentrations are 1.00M/L and 5.00M/L respectively) again, soaking for 30 minutes, taking out and drying, then roasting at 800 ℃ for 90 minutes under nitrogen to obtain the monolithic composite material, wherein the weight is shown in figure 11..
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.10g of tetraethylenepentamine, 0.20g of pentaethylenehexamine and 0.70g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 1:2: 7), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material with the weight of about 12.00g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the ozone catalytic decomposition stability is shown in FIG. 3, and the ozone catalytic decomposition performance is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, the carbon dioxide transmission curve is shown in FIG. 4, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 6
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 3:1: 1), putting the glass bottles into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and then putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, and then roasting the honeycomb ceramic-porous carbon composite material is obtained at 800 ℃ under the nitrogen atmosphere and the weight of about 11.00 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.10g of tetraethylenepentamine, 0.20g of pentaethylenehexamine and 0.70g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:3: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material with the weight of about 12.00g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 7
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is 1.00M/L and 5.00M/L respectively), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 6.00g of 3-methylpyrrole into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a baking oven with the temperature of 190 ℃ for reacting for 6 hours, taking out and putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is 1.00M/L and 5.00M/L respectively) again for soaking for 30 minutes, taking out and drying, and then roasting for 90 minutes at the temperature of 900 ℃ under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon monolithic composite material, wherein the weight of the honeycomb ceramic-porous carbon.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
the honeycomb ceramic-porous carbon integral composite material is put into 25m L methanol mixed solution containing 0.80g polyethyleneimine, ultrasonic treatment is carried out for 5 minutes, and then the honeycomb ceramic-porous carbon-organic amine integral composite material is put into a vacuum drying oven to remove the solvent, so that the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.60g is obtained, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 8
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid and the pyrophosphoric acid into a reaction kettle, transferring 4.00g of pyrrole, 0.50g of 2-methylpyrrole and 0.50g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 8:1: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and then putting into 20ml of mixed aqueous solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, and then obtaining the calcined honeycomb ceramic-porous carbon monolithic composite material with the weight of about 11.10g and weight of 11.10.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.50g of tetraethylenepentamine, 0.50g of pentaethylenehexamine and 0.10g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 5:5: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying oven to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material with the weight of about 12.20g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 9
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic into 20ml of phosphoric acid aqueous solution (the concentration is respectively 4.00M/L) to be soaked for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with phosphoric acid into a reaction kettle, transferring 5.00g of pyrrole into a glass bottle, putting the glass bottle into the reaction kettle, putting the reaction kettle into a 190 ℃ drying oven to react for 6 hours, taking out and putting into 20ml of phosphoric acid aqueous solution (the concentration is respectively 4.00M/L) again to be soaked for 30 minutes, taking out and drying, and then roasting for 90 minutes at 800 ℃ under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon integral composite material with the weight of about 11.10 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
the honeycomb ceramic-porous carbon integral composite material is put into a 25m L methanol mixed solution containing 1.10g of tetraethylenepentamine, ultrasonic treatment is carried out for 5 minutes, and then the honeycomb ceramic-porous carbon-organic amine integral composite material is put into a vacuum drying oven to remove the solvent, so that the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 12.20g is obtained, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Example 10
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic into 20ml of pyrophosphoric acid aqueous solution (the concentration is 5.00M/L) to be soaked for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with pyrophosphoric acid into a reaction kettle, transferring 5.00g of 2-methylpyrrole into a glass bottle, putting the glass bottle into the reaction kettle, putting the reaction kettle into a 190 ℃ oven to react for 6 hours, taking out and putting into 20ml of pyrophosphoric acid mixed solution (the concentration is 5.00M/L) again to be soaked for 30 minutes, taking out and drying, and then roasting at 900 ℃ for 90 minutes under nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon integral composite material with the weight of about 10.90 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
the honeycomb ceramic-porous carbon integral composite material is put into a 25m L methanol mixed solution containing 0.90g of pentaethylenehexamine, ultrasonic treatment is carried out for 5 minutes, and then the honeycomb ceramic-porous carbon-organic amine integral composite material is put into a vacuum drying oven to remove the solvent, so that the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.80g is obtained, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Comparative example 1
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, directly putting the cordierite honeycomb ceramic (about 10.00g) without loading phosphoric acid or pyrophosphoric acid on the surface into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a baking oven with the temperature of 190 ℃ for reacting for 6 hours, taking out the reaction kettle, putting the reaction kettle into a mixed solution of 20ml of phosphoric acid and pyrophosphoric acid (the concentration of 1.00M/L and 5.00M/L respectively) for soaking for 30 minutes, taking out and drying, and then roasting for 90 minutes at the temperature of 800 ℃ under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon monolithic.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.10g of tetraethylenepentamine, 0.05g of pentaethylenehexamine and 0.05g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:1: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying oven to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 10.40g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
Comparative example 2
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic into 20ml of mixed solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and directly roasting for 90 minutes at 800 ℃ under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon monolithic composite material, wherein the weight is about 11.30 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.30g of tetraethylenepentamine, 0.05g of pentaethylenehexamine and 0.05g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:1: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 12.60g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
Comparative example 3
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of pyrophosphate solution (the concentration is respectively 5.0M/L) to be soaked for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with phosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven to react for 6 hours, taking out and putting into 20ml of pyrophosphate solution (the concentration is 5.0M/L) again to be soaked for 30 minutes, taking out and drying, and then roasting at 800 ℃ for 90 minutes under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon integrated composite material, wherein the weight of about 10.80 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.40g of tetraethylenepentamine, 0.20g of pentaethylenehexamine and 0.20g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 2:1: 1), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.60g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
Comparative example 4
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of phosphoric acid solution (the concentration is 1.00M/L) to be soaked for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with phosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven to react for 6 hours, taking out and putting into 20ml of phosphoric acid solution (the concentration is 1.00M/L) again to be soaked for 30 minutes, taking out and drying, and then roasting at 800 ℃ for 90 minutes under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon monolithic composite material, wherein the weight of about 10.70 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.10g of tetraethylenepentamine, 0.20g of pentaethylenehexamine and 0.40g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 1:2: 4), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.40g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 5, and the catalytic decomposition performance of ozone is shown in Table 3.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 5, and the carbon dioxide adsorption reaction performance is shown in Table 4.
Comparative example 5
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid into a reaction kettle, transferring 1.00g of pyrrole, 2.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, the pyrrole, the 2-methylpyrrole and the 3-methylpyrrole are mixed according to the mass ratio of 1:2: 3) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and putting into 20ml of mixed solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, and then roasting the honeycomb ceramic-monolithic carbon composite material at 1200 ℃ for 90 minutes under the nitrogen atmosphere is obtained, and the porous carbon monolithic composite material is about 10.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
putting the honeycomb ceramic-porous carbon integral composite material into a mixed solution of 25m L methanol containing 0.10g of tetraethylenepentamine, 0.20g of pentaethylenehexamine and 0.20g of polyethyleneimine (namely, the tetraethylenepentamine, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 1:2: 2), carrying out ultrasonic treatment for 5 minutes, and then putting the mixture into a vacuum drying box to remove the solvent, thereby obtaining the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.00g, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Comparative example 6
(1) Preparing the honeycomb ceramic-porous carbon integral composite material:
weighing a piece of 200-mesh cordierite honeycomb ceramic (about 10.00g) with the diameter of 20mm and the height of 50mm, putting the cordierite honeycomb ceramic (about 10.00g) into 20ml of mixed solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, putting the honeycomb ceramic loaded with the phosphoric acid into a reaction kettle, transferring 3.00g of 2-methylpyrrole and 3.00g of 3-methylpyrrole (namely, mixing the 2-methylpyrrole and the 3-methylpyrrole according to the mass ratio of 1: 1) into a glass bottle, putting the glass bottle into the reaction kettle together, putting the reaction kettle into a 190 ℃ oven for reacting for 6 hours, taking out and putting into 20ml of mixed solution of phosphoric acid and pyrophosphoric acid (the concentration is respectively 1.00M/L and 5.00M/L), soaking for 30 minutes, taking out and drying, and then roasting for 90 minutes at 800 ℃ under the nitrogen atmosphere to obtain the honeycomb ceramic-porous carbon monolithic composite material with the weight of about 10.60 g.
(2) Preparing the honeycomb ceramic-porous carbon-organic amine integral composite material:
the honeycomb ceramic-porous carbon integral composite material is put into a mixed solution of 25m L methanol containing 0.30g of pentaethylenehexamine and 0.3g of polyethyleneimine (namely, the pentaethylenehexamine and the polyethyleneimine are mixed according to the mass ratio of 1: 1), ultrasonic treatment is carried out for 5 minutes, and then the mixture is put into a vacuum drying oven to remove the solvent, so that the honeycomb ceramic-porous carbon-organic amine integral composite material weighing about 11.20g is obtained, namely the carbon dioxide adsorbent.
(3) Ozone catalytic decomposition performance test:
the catalyst performance test was the same as in example 1, and the catalytic decomposition performance of ozone is shown in Table 1.
(4) Sorbent performance testing:
the adsorbent performance test was the same as in example 1, and the carbon dioxide adsorption reaction performance is shown in Table 2.
Table 1: the reaction performance of the honeycomb ceramic-porous carbon in examples 1 to 10 for catalytic decomposition reaction of ozone (expressed as the conversion rate of ozone at 10.5 hours of catalytic continuous reaction, i.e., the concentration of ozone that has been converted divided by the concentration of ozone before conversion)
As can be seen from Table 1, the honeycomb ceramic-porous carbon monolithic composite catalysts of examples 1-8 all showed good catalytic decomposition performance for ozone, and due to the porous structure of the honeycomb ceramic, the catalysts can be used many at a time, solving the problem of pressure drop. In particular, example 5 was the highest in catalytic efficiency, with the ozonolysis conversion of 60.13% for one catalyst, 80.08% for two catalysts and 91.46% for three catalysts at room temperature. As can be seen from comparative examples 1 to 4 of Table 3, if the mixed solution of phosphoric acid and pyrophosphoric acid is not used or only one is used in the preparation of the honeycomb ceramic-porous carbon monolithic composite, the catalyst catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite is decreased; as can be seen from comparative example 5, too high a carbonization temperature (i.e., from the original carbonization at 800 ℃ to the carbonization at 1200 ℃), the catalytic performance of the prepared catalyst is also reduced; as can be seen from comparative example 6, if only one of pyrrole, 2-methylpyrrole and 3-methylpyrrole is selected, the catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite is also reduced.
Table 2: carbon dioxide adsorption performance of the adsorbents in examples 1 to 10 (expressed in terms of carbon dioxide adsorption amount per unit mass of the adsorbent in mmol/g. the specific algorithm is carbon dioxide adsorption amount divided by (sum of mass of porous carbon and organic amine), and honeycomb ceramics is used as a carrier, the mass of which is not calculated within the total mass of the adsorbent.)
As can be seen from table 2, the honeycomb ceramic-porous carbon monolithic composites of examples 1 to 8 all showed good carbon dioxide adsorption performance after loading organic amine, and due to the porous structure of the honeycomb ceramic, the adsorbent can be used many blocks at a time, solving the pressure drop problem. Particularly, the carbon dioxide adsorption performance of example 5 was the highest, and at room temperature, the carbon dioxide adsorption performance of one adsorbent was 3.09mmol/g, the carbon dioxide adsorption performance of two adsorbents was 2.61mmol/g, and the carbon dioxide adsorption performance of three adsorbents was 2.30 mmol/g. As can be seen from comparative examples 1 to 4 of Table 4, if the mixed solution of phosphoric acid and pyrophosphoric acid is not used or only one is used in the preparation of the honeycomb ceramic-porous carbon monolithic composite, the catalyst catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite is decreased; as can be seen from comparative example 5, too high a carbonization temperature (i.e., from the original carbonization at 800 ℃ to the carbonization at 1200 ℃), the catalytic performance of the prepared catalyst is also reduced; as can be seen from comparative example 6, if only two of pyrrole, 2-methylpyrrole and 3-methylpyrrole are selected, the catalytic performance of the prepared honeycomb ceramic-porous carbon monolithic composite is also reduced.
Table 3: example 5, comparative examples 1-6 reaction Performance for catalytic decomposition reaction of ozone (expressed as conversion of ozone at 10.5h of catalytic continuous reaction, i.e. concentration of ozone that has been converted divided by concentration of ozone before conversion)
Table 4: comparative carbon dioxide adsorption performance (expressed in terms of carbon dioxide adsorption amount per unit mass of adsorbent, in mmol/g. the specific algorithm is carbon dioxide adsorption amount divided by (sum of mass of porous carbon and organic amine), honeycomb ceramic is used as a carrier, and mass thereof is not calculated within total mass of adsorbent.) in example 5 and comparative examples 1 to 6
The following figures 1-6 are further illustrated by way of analysis:
in FIG. 1, FIG. 1a shows a raw material of honeycomb ceramics used in the present invention, which is light yellow in color; FIG. 1b is a schematic representation of a honeycomb ceramic-porous carbon monolithic composite made in example 5, black in color; it is shown that example 5 can conveniently form a layer of porous carbon film on the honeycomb ceramic, and the porous carbon film and the honeycomb ceramic are closely contacted and are not easy to fall off.
In FIG. 2, FIG. 2a is a SEM photograph of a cross-section of a honeycomb ceramic raw material used in example 5, showing that the honeycomb ceramic structure is a cellular material; fig. 2b is a scanning electron microscope photograph of a cross section of the honeycomb ceramic-porous carbon monolithic composite prepared in example 5, and it can be seen from the scanning cross section of the composite that a porous carbon film (a cross section of porous carbon at the upper side in fig. 2 b) is successfully formed on the surface of the honeycomb ceramic (a cross section of honeycomb ceramic at the lower side in fig. 2 b), and the two are in close contact and are not easy to fall off.
Fig. 3 is a transmission electron microscope photograph of a cross section of the honeycomb ceramic-porous carbon monolithic composite prepared in example 5, and it can be seen that a porous carbon film is successfully formed on the honeycomb ceramic in example 5, and the contact between the two is very close and is not easy to fall off.
In fig. 4, a spectrum a is an X-ray photoelectron energy spectrum of a honeycomb ceramic raw material, and a spectrum b is an X-ray photoelectron energy spectrum of the honeycomb ceramic-porous carbon monolithic composite material prepared in example 5, wherein N, C, P and other elements are added on the surface of the honeycomb ceramic in comparison with the change ratio of the two spectra, so that it can be inferred that N, P doped porous carbon material is generated on the surface of the honeycomb ceramic.
In fig. 5, maps a, b, c are graphs comparing the removal stability of ozone using 1, 2 and 3 honeycomb ceramic-porous carbon monolithic composite catalysts prepared in example 5, respectively; it can be seen that the catalyst is not easy to block because of the porous structure, so that the pressure drop problem can not be generated even if the amount of the catalyst is increased, and the pressure drop problem of the powder sample is solved. Wherein, the initial catalytic activity of the catalyst using 3 pieces of catalyst is 99.9%, and the catalytic conversion rate of ozone is still maintained at 86.9% after 30 hours of reaction. Thus, the number of the first and second electrodes,
in FIG. 6, spectra a, b, c are graphs showing the breakthrough of carbon dioxide adsorption performance of one, two and three honeycomb ceramic-porous carbon-organic amine monolithic composite adsorbents prepared in example 5 using 1, 2 and 3 blocks, respectively; it can be seen that the adsorbent is in a porous structure and is not easy to block, so that the amount of the adsorbent is increased immediately, the pressure drop problem is not generated, and the pressure drop problem of the powder sample is solved. From the breakthrough curves of FIG. 5, it can be calculated that the unit adsorption amount of the adsorbent was 3.09mmol/g using one adsorbent, 2.61mmol/g using two adsorbents, and 2.30mmol/g using three adsorbents.
In conclusion, the honeycomb ceramic-porous carbon monolithic catalyst has high catalytic decomposition and oxidation activity on ozone and good stability, and the catalyst has simple preparation process and good reproducibility and can solve the problem of pressure drop caused by large-scale application of the catalyst. The honeycomb ceramic-porous carbon-organic amine integral composite material as an adsorbent shows higher carbon dioxide adsorption performance, and the adsorbent has simple preparation process and good reproducibility, and can solve the problem of pressure drop caused by large-scale application of the adsorbent in the actual industry.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any changes and alterations made without inventive step within the spirit and scope of the claims are intended to fall within the scope of the invention.
Claims (10)
1. The monolithic catalyst is characterized by being a monolithic honeycomb ceramic-porous carbon composite material, and consisting of a carrier and an active component, wherein the content of the active component is 1-15 wt% of the total mass of the monolithic catalyst, the carrier is monolithic honeycomb ceramic, and the active component is porous carbon doped with nitrogen and phosphorus.
2. The monolithic honeycomb ceramic-porous carbon catalyst according to claim 1, wherein the active component is supported by a chemical vapor polymerization and high temperature carbonization activation method, and the carrier is monolithic cordierite honeycomb ceramic.
3. A method for preparing the honeycomb ceramic-porous carbon monolithic catalyst of claim 1 or 2, comprising the steps of:
step 1, loading phosphoric acid and/or pyrophosphoric acid on the surface of integral honeycomb ceramic by an impregnation method, drying, and generating a layer of polypyrrole compound on the surface of integral honeycomb ceramic by a chemical vapor polymerization method at 140-220 ℃ in a reaction kettle;
2, loading phosphoric acid and/or pyrophosphoric acid by an impregnation method again;
and 3, converting the polypyrrole compound into a porous carbon material by a high-temperature carbonization activation method, wherein the high-temperature carbonization activation temperature is 500-1000 ℃, and the high-temperature carbonization activation time is 1-3 hours, so that the honeycomb ceramic-porous carbon integral catalyst is obtained.
4. The method according to claim 3, wherein the precursor of the polypyrrole-based compound is any one of pyrrole, 2-methylpyrrole, and 3-methylpyrrole, or a mixture of any two or more of them.
5. The production method according to claim 3 or 4, wherein the monolithic honeycomb ceramic is a monolithic cordierite honeycomb ceramic.
6. Use of a honeycomb ceramic-porous carbon monolithic catalyst according to claim 1 or 2 in ozonolysis.
7. The honeycomb ceramic-porous carbon integral adsorbent is characterized by consisting of an adsorbent carrier and an adsorbent active component, wherein the adsorbent carrier is a honeycomb ceramic-porous carbon integral composite material, and the adsorbent active component is organic amine.
8. The monolithic honeycomb ceramic-porous carbon adsorbent of claim 7, wherein the organic amine is loaded by co-impregnation method, and the organic amine is one of tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine or a mixture of two or more of the above.
9. The preparation method of the honeycomb ceramic-porous carbon monolithic adsorbent according to claim 7 or 8, characterized by immersing the honeycomb ceramic-porous carbon monolithic composite material in a methanol mixed solution of tetraethylenepentamine, pentaethylenehexamine and polyethyleneimine in a certain mass ratio of (0.1-5): 0.1-5, carrying out ultrasonic treatment, taking out, and removing the solvent in a vacuum drying oven to obtain the honeycomb ceramic-porous carbon-organic amine monolithic composite material.
10. Use of the honeycomb ceramic-porous carbon monolithic adsorbent according to claim 7 or 8 for carbon dioxide adsorption.
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