CN117299082A - Preparation and evaluation method of nitrogen-doped renewable adsorption CNCL material - Google Patents
Preparation and evaluation method of nitrogen-doped renewable adsorption CNCL material Download PDFInfo
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- CN117299082A CN117299082A CN202311046264.6A CN202311046264A CN117299082A CN 117299082 A CN117299082 A CN 117299082A CN 202311046264 A CN202311046264 A CN 202311046264A CN 117299082 A CN117299082 A CN 117299082A
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000011156 evaluation Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000012876 carrier material Substances 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 238000003795 desorption Methods 0.000 claims description 40
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 31
- 239000010935 stainless steel Substances 0.000 claims description 31
- 229920000877 Melamine resin Polymers 0.000 claims description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
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- 238000010926 purge Methods 0.000 claims description 7
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- 231100000167 toxic agent Toxicity 0.000 claims description 6
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- 238000011068 loading method Methods 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 8
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
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- 239000003463 adsorbent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- CZSOUHCUPOPPRC-UHFFFAOYSA-N 3-phenylphthalaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1C=O CZSOUHCUPOPPRC-UHFFFAOYSA-N 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
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- 150000004753 Schiff bases Chemical class 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
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- 239000002575 chemical warfare agent Substances 0.000 description 1
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- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 229960001553 phloroglucinol Drugs 0.000 description 1
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N phloroglucinol aldehyde Natural products OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- G01F—MEASURING VOLUME, VOLUME FLOW, MASS FLOW OR LIQUID LEVEL; METERING BY VOLUME
- G01F1/00—Measuring the volume flow or mass flow of fluid or fluent solid material wherein the fluid passes through a meter in a continuous flow
- G01F1/05—Measuring the volume flow or mass flow of fluid or fluent solid material wherein the fluid passes through a meter in a continuous flow by using mechanical effects
- G01F1/34—Measuring the volume flow or mass flow of fluid or fluent solid material wherein the fluid passes through a meter in a continuous flow by using mechanical effects by measuring pressure or differential pressure
- G01F1/36—Measuring the volume flow or mass flow of fluid or fluent solid material wherein the fluid passes through a meter in a continuous flow by using mechanical effects by measuring pressure or differential pressure the pressure or differential pressure being created by the use of flow constriction
- G01F1/40—Details of construction of the flow constriction devices
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to the field of preparation of adsorption materials, in particular to a preparation and evaluation method of a nitrogen-doped renewable adsorption CNCL material; the method comprises the following steps: (1) preparing an organic amine solution; (2) Pouring an organic amine solution serving as an impregnating solution into the carrier material, and standing to enable the impregnating solution to fully impregnate the carrier material to obtain an impregnated carrier material; (3) drying the impregnated carrier material; (4) Transferring the dried impregnated carrier material into a porcelain crucible, placing in a tube furnace, forming nitrogen atmosphere in the tube furnace by high-purity nitrogen replacement, continuously introducing nitrogen, and introducing N into the tube furnace 2 And (3) carrying out temperature programming calcination under protection to obtain the nitrogen-doped renewable adsorption CNCL material. The preparation process of the invention is simple, no heavy metal pollution, environment-friendly and few preparation steps, and the prepared material can realize the reproducible adsorption of the CNCL by utilizing weak chemical adsorption, and can realize the reproducible cyclic adsorption of the CNCL for 5 times without reducing the performance.
Description
Technical Field
The invention relates to the field of preparation of adsorption materials, in particular to a preparation and evaluation method of a nitrogen-doped renewable adsorption CNCL material.
Background
CNCL belongs to highly toxic gas, has small molecular weight and high volatility, and is difficult to protect, so that the CNCL becomes a chemical weapon and causes injury to personnel. The protection of the toxic gas diffused in the air at present mainly comprises the steps of impregnating active carbon with metal oxide, TEDA and the like, and is limited by adsorption capacity. In addition, because of the high toxicity of the CNCL, the research on the renewable protection of the CNCL is hardly reported at the present stage, so that a novel adsorption material which can adsorb the CNCL and has renewable performance is required to be developed to replace the adsorption material mainly based on impregnated carbon in the current air purification system, and the technical support is provided for the material for the renewable air purification system.
Since the renewable adsorption material of the CNCL is not reported, the renewable adsorption material of the CNCL can only be explored by referring to similar substances. As known in the literature, nitrogen doped materials are useful for CO 2 The gas realizes the renewable adsorption effect by analyzing CO 2 The molecules have similar linear structures with the CNCL molecules, and the molecules are similar in size (CNCL 2.83A, CO 2.32A) and belong to the following groupsIn acid gas. Through further literature research, the nitrogen doped carbon-based material can adsorb other acid gases H 2 S、NO X And organic chlorine pollutants in the water body. Research on adsorption of CO as Zhou Zhihui et al 2 The renewable adsorption material takes melamine, phloroglucinol and formaldehyde as raw materials, and synthesizes melamine phenolic fiber through hydrothermal polycondensation reaction, and the material is used for CO 2 Carrying out adsorption separation; gu Shixiao and the like prepare microporous organic materials for CO by reacting melamine with o-phthalaldehyde, p-phthalaldehyde and biphenyl-dicarboxaldehyde respectively 2 And (5) carrying out adsorption separation. The method has the characteristics of more reaction substances and complicated process. Li Qiaoyan et al study of NO X The adsorption material is dissolved in 80% ethanol through melamine to form suspension, and the suspension is used for impregnating the coal-based activated carbon, and then drying and calcining are carried out. The method introduces ethanol solution which is easy to be inflammable and explosive in the actual production process, and the alkaline group of the nitrogen doped material can adsorb NO and adsorb NO in O 2 Oxidation of NO to NO in the presence of 2 . The porous Schiff base polymer composite material supported by the nitrogen carbide structure in patent CN 107216605A of Liao Guiying and the like can adsorb organic chlorine pollutants in a water body, and can be washed and desorbed for recycling after adsorption. However, in the process of synthesizing the polymer composite material, melamine, terephthalaldehyde, nitrogen carbide and dimethyl sulfoxide are added, an anhydrous and anaerobic system is also needed, the synthesis conditions are harsh, and the operation steps in the separation and purification process are complex.
The existing protective material for CNCL is impregnated activated carbon, contains various metal oxides, TEDA and the like, realizes single protection through chemical reaction with the CNCL, and cannot be regenerated in situ. Through the related literature data and patent inquiry, the corresponding evaluation device of the renewable adsorption material of the related CNCL and the renewable adsorption material of the CNCL is not reported. Therefore, the adsorption effect of the nitrogen doped compound on the acid gas and the chlorine-containing compound is required to be used for designing a material which has simple synthesis process and regenerable adsorption on the CNCL, and the adsorption and desorption performance of the regenerable adsorption material on the CNCL is evaluated in a corresponding evaluation mode.
Disclosure of Invention
The invention provides a material for renewable adsorption of CNCL and an evaluation device and an evaluation method for evaluating the renewable adsorption material, and the synthesis method and the evaluation means of the renewable adsorption material can provide design parameters for the renewable adsorption device of CNCL.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the nitrogen-doped renewable adsorption CNCL material comprises the following steps of:
(1) Preparing an organic amine solution;
(2) Pouring an organic amine solution serving as an impregnating solution into the carrier material, and standing to enable the impregnating solution to fully impregnate the carrier material to obtain an impregnated carrier material;
(3) Drying the impregnated carrier material;
(4) Transferring the dried impregnated carrier material into a porcelain crucible, placing in a tube furnace, forming nitrogen atmosphere in the tube furnace by replacement of 99.999% high-purity nitrogen, continuously introducing nitrogen, and introducing N 2 And (3) carrying out temperature programming calcination under protection to obtain the nitrogen-doped renewable adsorption CNCL material.
Further, the organic amine is melamine or urea.
Further, the carrier material is activated carbon, carbon fiber, or other porous adsorption material.
Further, in the step (2), if the organic amine is melamine, the mass of the melamine is 2-3% of the mass of the carrier material, and if the organic amine is urea, the mass of the urea is 3-5% of the mass of the carrier material.
Further, the temperature programming and calcining conditions in the step (4) are that the temperature is raised to 850 ℃ at a temperature raising rate of 5 ℃/min, and the temperature is kept for 120min.
Further, the standing time in the step (2) is 3 hours.
The invention also provides an evaluation method of the renewable adsorption CNCL material obtained by the preparation method, and an adsorption evaluation device and a desorption evaluation device are respectively adopted to carry out adsorption and desorption measurement;
the adsorption evaluation device comprises a compressed air filter, a humidity regulator, a dry and wet ball thermometer, a mixed ball, a toxic gas steel cylinder and a drying tower which are sequentially connected together through pipelines, wherein the drying tower is also communicated with the humidity regulator; the air outlet end of the mixing ball is also connected with a plurality of stainless steel measuring pipes which are connected in parallel, and one end of each stainless steel measuring pipe is provided with an indicator; a pore plate flowmeter is connected between the dry-wet ball thermometer and the mixing ball, a pore plate flowmeter is connected between the toxic gas steel cylinder and the drying tower, and a pore plate flowmeter is also connected between the mixing ball and the stainless steel measuring tube;
the desorption evaluation device comprises an air generator, a mass flowmeter, a stainless steel measuring tube and a vacuum pump which are sequentially connected together through pipelines, wherein a water bath kettle is arranged at the stainless steel measuring tube;
placing a renewable adsorption CNCL material in a stainless steel measuring tube for measurement, taking down the stainless steel measuring tube when a toxic agent penetrates through an indicator to change color, then carrying out desorption treatment on the adsorption material, connecting the taken down stainless steel measuring tube into a desorption evaluation device, setting the water bath temperature to 96 ℃, setting the flow of a mass flowmeter to 200mL/min, and turning on a vacuum pump and the mass flowmeter to carry out vacuum desorption and small flow purging desorption on the adsorption material for 20min; and after the desorption is completed, loading the stainless steel measuring tube into the adsorption evaluation device again for adsorption, and when the toxic agent penetrates through the indicator to change color, performing desorption evaluation again, namely vacuum desorption and small-flow purging desorption, repeating the steps, and performing a plurality of cycles.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation process of the invention is simple, no heavy metal pollution, environment-friendly and few preparation steps, and the prepared material can realize the reproducible adsorption of the CNCL by utilizing weak chemical adsorption, and can realize the reproducible cyclic adsorption of the CNCL for 5 times without reducing the performance.
2. Meanwhile, the invention also provides an evaluation method of the evaluation device, which creatively utilizes the vacuum+hot air back-blowing desorption technology, and can evaluate the adsorption and desorption performance of the adsorbent so as to evaluate the reproducibility of the adsorption material; the evaluation device can realize in-situ regeneration of the adsorption material, does not need to pour out and regenerate toxic substances, and is beneficial to evaluation. The evaluation device disclosed by the invention is simple to operate and high in practicability, and can provide reference significance for the subsequent renewable air purification device.
3. The invention has the advantages of green and energy-saving performance, simple process steps, and cheap materials.
Drawings
FIG. 1 is a schematic diagram of the adsorption evaluation apparatus according to the present invention.
Fig. 2 is a schematic diagram of the desorption evaluation device according to the present invention.
The figures are labeled as follows:
1-compressed air filter, 2-humidity regulator, 3-dry and wet ball thermometer, 4-orifice flowmeter, 5-mixing ball, 6-poison gas steel cylinder, 7-drying tower, 8-stainless steel measuring tube, 9-indicator, 10-air generator, 11-mass flowmeter, 12-vacuum pump, 13-water bath.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Example 1
The preparation method of the nitrogen-doped renewable adsorption CNCL material comprises the following steps of:
weighing a certain amount of activated carbon, placing the activated carbon in a beaker, weighing a certain amount of melamine (the mass of the melamine is 2% of the mass of the activated carbon) solid, adding boiling water, stirring and heating on a flat heating furnace until the melamine is completely dissolved, then rapidly pouring the completely dissolved melamine solution into the activated carbon, standing for 3 hours to enable the impregnating solution to fully impregnate the activated carbon, transferring substances in the beaker into a square magnetic disk, placing the square magnetic disk in an electrothermal blowing drying oven for heating, and setting the temperature to be 110 ℃ and the drying time to be 2 hours. After the impregnated carbon is completely dried, the impregnated carbon is transferred into a porcelain crucible and placed in a tube furnace to pass through 99.999 percent ofHigh-purity nitrogen is replaced to form nitrogen atmosphere in the tube furnace and continuously introducing nitrogen into the tube furnace, and the nitrogen is replaced by N 2 And (5) carrying out temperature programming calcination under protection. Setting the temperature of programmed heating, heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 120min, and taking out the sample after the sample is naturally cooled to room temperature to obtain the modified nitrogen-doped renewable adsorption material.
Example 2
Weighing a certain amount of active carbon, placing the active carbon in a beaker, weighing a certain amount of urea (the mass of the urea is 5% of the mass of the active carbon) to prepare a solution, then pouring the urea solution into the active carbon rapidly, standing for 3 hours to enable the impregnating solution to fully impregnate the active carbon, then transferring substances in the beaker into a square magnetic disc, placing the square magnetic disc in an electrothermal blowing drying oven for heating, and setting the temperature to be 110 ℃ and the drying time to be 2 hours. After the impregnated carbon is completely dried, transferring the impregnated carbon into a porcelain crucible, placing the porcelain crucible in a tube furnace, forming nitrogen atmosphere in the tube furnace through high-purity nitrogen replacement of 99.999%, continuously introducing nitrogen, and introducing nitrogen into the tube furnace to obtain a ceramic material 2 And (5) carrying out temperature programming calcination under protection. Setting the temperature of programmed heating, heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 120min, and taking out the sample after the sample is naturally cooled to room temperature to obtain the modified nitrogen-doped renewable adsorption material.
Example 3
Weighing a certain amount of carbon fiber sample, placing the carbon fiber sample in a beaker, weighing a certain amount of melamine (the mass of the melamine is 3% of the mass of the carbon fiber sample), adding boiling water, stirring and heating on a flat heating furnace until the melamine is completely dissolved, then rapidly pouring the completely dissolved melamine solution into the carbon fiber, standing for 3 hours to enable the impregnating solution to fully impregnate the carbon fiber, transferring substances in the beaker into a square magnetic disk, placing the square magnetic disk in an electrothermal blowing drying box for heating, and setting the temperature to be 110 ℃ and the drying time to be 2 hours. After the impregnated carbon fiber is completely dried, transferring the impregnated carbon fiber into a porcelain crucible, placing the porcelain crucible into a tube furnace, the nitrogen atmosphere is formed in the tube furnace by the replacement of 99.999 percent of high-purity nitrogen, and the nitrogen is continuously introduced into the tube furnace, and the nitrogen is replaced by N 2 And (5) carrying out temperature programming calcination under protection. Setting the temperature of programmed heating, heating to 850 ℃ at a heating rate of 5 ℃/min, and keeping constantAnd (3) heating for 120min, and taking out the sample after the sample is naturally cooled to room temperature to obtain the modified nitrogen-doped renewable adsorption material.
Example 4
Weighing a certain amount of carbon fiber sample, placing the carbon fiber sample in a beaker, weighing a certain amount of urea (the mass of the urea is 4% of the mass of the carbon fiber sample) to prepare a solution, then pouring the urea solution into active carbon rapidly, standing for 3 hours to enable the impregnating solution to fully impregnate the carbon fiber, transferring substances in the beaker into a square magnetic disk, placing the square magnetic disk in an electrothermal blowing drying oven for heating, and setting the temperature to be 110 ℃ and the drying time to be 2 hours. After the impregnated carbon is completely dried, transferring the impregnated carbon fiber into a porcelain crucible, placing the porcelain crucible into a tube furnace, forming a nitrogen atmosphere in the tube furnace through high-purity nitrogen replacement of 99.999%, continuously introducing nitrogen, and introducing nitrogen into the tube furnace to obtain a ceramic fiber, wherein the ceramic fiber is prepared by the steps of 2 And (5) carrying out temperature programming calcination under protection. Setting the temperature of programmed heating, heating to 850 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 120min, and taking out the sample after the sample is naturally cooled to room temperature to obtain the modified nitrogen-doped renewable adsorption material.
Example 5
This example provides an apparatus and an evaluation method for evaluating the adsorption-desorption performance of the CNCL renewable adsorption material prepared in examples 1 to 4. The evaluation device mainly relies on the principles of Pressure Swing Adsorption (PSA) and Temperature Swing Adsorption (TSA), i.e., the adsorbate enters a stainless steel measuring tube filled with the adsorbate through a measuring tube, and is connected to an adsorption evaluation device system (as shown in fig. 1) to perform normal temperature and pressure adsorption, and when reaching an adsorption penetration point, the stainless steel measuring tube is removed and connected to a desorption device (as shown in fig. 2). Vacuum desorption and clean hot air blowing are carried out, so that the adsorbed adsorbents in the adsorbent are removed from the system, and the aim of regeneration is fulfilled.
The adsorption material evaluation device comprises a compressed air filter 1, a humidity regulator 2, a wet and dry bulb thermometer 3, a mixing bulb 5, a toxic gas steel cylinder 6 and a drying tower 7 which are sequentially connected together through pipelines, wherein the drying tower 7 is also communicated with the humidity regulator 2; the air outlet end of the mixing ball 5 is also connected with a plurality of stainless steel measuring pipes 8 (stainless steel L=5cm, D=1cm, height-diameter ratio: 5:1) which are connected in parallel, and one end of each stainless steel measuring pipe 8 is provided with an indicator 9; an orifice plate flowmeter 4 is connected between the dry-wet bulb thermometer 3 and the mixing bulb 5, an orifice plate flowmeter 4 is connected between the toxic gas steel cylinder 6 and the drying tower 7, and an orifice plate flowmeter 4 is also connected between the mixing bulb 5 and the stainless steel measuring tube 8;
the desorption evaluation device (shown in figure 2) comprises an air generator 10, a mass flowmeter 11, a stainless steel measuring tube 8 and a vacuum pump 12 which are sequentially connected together through pipelines, wherein a water bath 13 is arranged at the stainless steel measuring tube 8; (the water bath 13 can be replaced by an air heater, the air and poison gas paths can be replaced by a gas distribution cabinet, and the indicator 9 can be detected by a photoacoustic spectrometer and the aim of the invention can be fulfilled).
Placing a renewable adsorption CNCL material in a stainless steel measuring tube 8 for measurement, taking down the stainless steel measuring tube 8 when a toxic agent penetrates through an indicator to change color, then carrying out desorption treatment on the adsorption material, connecting the taken down stainless steel measuring tube 8 into a desorption evaluation device, setting the water bath temperature to 96 ℃, setting the flow of a mass flowmeter to 200mL/min, opening a vacuum pump 12 and the mass flowmeter 11, and carrying out vacuum desorption and small flow purging desorption on the adsorption material for 20min; after the desorption is completed, loading the stainless steel measuring tube 8 into the adsorption evaluation device again for adsorption, and when the toxic agent penetrates through the indicator to change color, performing desorption evaluation again, namely vacuum desorption and small flow purging desorption, repeating the steps, and performing a plurality of cycles.
Experiment verification
The invention prepares the nitrogen-doped renewable adsorption material by taking activated carbon as a carrier to impregnate melamine/urea, and takes carbon fiber as the carrier to impregnate melamine/urea. And a set of evaluation device for evaluating the reproducible adsorption and desorption of the nitrogen-doped material is designed. The device was used to verify the regenerability of nitrogen-doped adsorbent materials. Experiments prove that the evaluation device has practicability and applicability, and can evaluate the regenerability of the nitrogen-doped material well. In a specific experiment, the nitrogen-doped material is loaded into the evaluation device, and is evaluated in an adsorption-desorption repeated cycle experiment according to the mode of adsorption+vacuum+purging, and is circulated for 5 times, so that the reproducibility of the nitrogen-doped material is verified, and the evaluation result is shown in the following table 1. In the experiment, the 13X molecular sieve and the 13X molecular sieve-melamine sample are evaluated by the evaluation device for comparison, and the experimental result shows that the nitrogen-doped carbon-based material can realize the reproducible adsorption of the CNCL. Meanwhile, through the evaluation device, the working adsorption capacity, desorption efficiency and other parameters of the nitrogen-doped renewable adsorption material can be obtained, and various parameters obtained through evaluation provide design parameters for the design of a subsequent renewable gas purification device.
Therefore, the experiment verifies that the evaluation device has feasibility and applicability, and the nitrogen doped carbon-based material can realize the reproducible adsorption of the CNCL. The evaluation device can also perform an evaluation experiment of the renewable adsorption of other materials needing heating desorption, evaluate and screen out the suitable renewable adsorption materials, and obtain corresponding condition parameters. Providing reference meaning for the gas purifying device.
TABLE 1 multiple adsorption of CNCL time by regenerable adsorbent materials
Claims (7)
1. The preparation method of the nitrogen-doped renewable adsorption CNCL material is characterized by comprising the following steps of:
(1) Preparing an organic amine solution;
(2) Pouring an organic amine solution serving as an impregnating solution into the carrier material, and standing to enable the impregnating solution to fully impregnate the carrier material to obtain an impregnated carrier material;
(3) Drying the impregnated carrier material;
(4) Transferring the dried impregnated carrier material into a porcelain crucible, placing into a tube furnace, and replacing with 99.999% high-purity nitrogenForming a nitrogen atmosphere in the tube furnace, continuously introducing nitrogen, and introducing nitrogen into the tube furnace 2 And (3) carrying out temperature programming calcination under protection to obtain the nitrogen-doped renewable adsorption CNCL material.
2. The method for preparing the nitrogen-doped renewable adsorption CNCL material according to claim 1, wherein the organic amine is melamine or urea.
3. The method for preparing a nitrogen-doped regenerable adsorptive CNCL material according to claim 1, wherein the carrier material is activated carbon, carbon fiber, or other porous adsorptive material.
4. The method for preparing the nitrogen-doped renewable adsorption CNCL material according to claim 1, wherein in the step (2), if the organic amine is melamine, the mass of the melamine is 2-3% of the mass of the carrier material, and if the organic amine is urea, the mass of the urea is 3-5% of the mass of the carrier material.
5. The method for preparing the nitrogen-doped renewable adsorption CNCL material according to claim 1, wherein the temperature programming and calcining conditions in the step (4) are that the temperature is raised to 850 ℃ at a temperature raising rate of 5 ℃/min, and the temperature is kept for 120min.
6. The method for preparing the nitrogen-doped renewable adsorption CNCL material according to claim 1, wherein the standing time in the step (2) is 3 hours.
7. An evaluation method for the renewable adsorption CNCL material obtained by the preparation method according to claim 1, which is characterized in that an adsorption evaluation device and a desorption evaluation device are adopted to perform adsorption and desorption measurement respectively;
the adsorption evaluation device comprises a compressed air filter (1), a humidity regulator (2), a dry-wet ball thermometer (3), a mixing ball (5), a toxic gas steel cylinder (6) and a drying tower (7) which are sequentially connected together through pipelines, wherein the drying tower (7) is also communicated with the humidity regulator (2); the air outlet end of the mixing ball (5) is also connected with a plurality of stainless steel measuring pipes (8) which are connected in parallel, and one end of each stainless steel measuring pipe (8) is provided with an indicator (9); an orifice plate flowmeter (4) is connected between the dry-wet ball thermometer (3) and the mixing ball (5), an orifice plate flowmeter (4) is connected between the toxic gas steel cylinder (6) and the drying tower (7), and an orifice plate flowmeter (4) is also connected between the mixing ball (5) and the stainless steel measuring tube (8);
the desorption evaluation device comprises an air generator (10), a mass flowmeter (11), a stainless steel measuring tube (8) and a vacuum pump (12) which are sequentially connected together through pipelines, wherein a water bath pot (13) is arranged at the stainless steel measuring tube (8);
placing a renewable adsorption CNCL material in a stainless steel measuring tube (8) for measurement, taking down the stainless steel measuring tube (8) when a toxic agent penetrates through an indicator to change color, then carrying out desorption treatment on the adsorption material, connecting the taken down stainless steel measuring tube (8) into a desorption evaluation device, setting the water bath temperature to 96 ℃, setting the flow of a mass flowmeter to 200mL/min, and opening a vacuum pump (12) and the mass flowmeter (11), so as to carry out vacuum desorption and small flow purging desorption on the adsorption material for 20min; and after the desorption is completed, loading the stainless steel measuring tube (8) into the adsorption evaluation device again for adsorption, and when the toxic agent penetrates through the indicator to change color, performing desorption evaluation again, namely vacuum desorption and low-flow purging desorption, and repeating the steps for a plurality of times.
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