CN110015662B - Adsorb CO2Preparation method of nitrogen-doped porous carbon material - Google Patents

Adsorb CO2Preparation method of nitrogen-doped porous carbon material Download PDF

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CN110015662B
CN110015662B CN201910337194.7A CN201910337194A CN110015662B CN 110015662 B CN110015662 B CN 110015662B CN 201910337194 A CN201910337194 A CN 201910337194A CN 110015662 B CN110015662 B CN 110015662B
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nitrogen
porous carbon
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polyurethane foam
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CN110015662A (en
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葛超
杨颂
卢建军
刘妙青
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Taiyuan University of Technology
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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
    • B01D53/02—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
    • 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
    • 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
    • B01J20/28—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
    • B01J20/28052—Several layers of identical or different sorbents stacked in a housing, e.g. in a column
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention relates to the field of porous carbon materials, in particular to a method for adsorbing CO2The method for preparing the nitrogen-doped porous carbon material. Adsorb CO2Crushing waste polyurethane foam into particles of 2 mm x 2 mm-5 mm x 5 mm, then placing the particles into a quaternary ammonium base aqueous solution with the mass percent of 25% for dipping treatment for 1-10 h, and after the dipping treatment, carrying out vacuum drying for 10-30 h at 50-80 ℃; impregnating a polyurethane foam impregnated with a quaternary ammonium base in N2Carrying out low-temperature chemical activation treatment in the atmosphere; directly subjecting the activated product to CO without cooling and acid washing2Physical activation, namely obtaining the adsorbed CO with large specific surface area and micropore volume and rich nitrogen content2The porous carbon material is doped with nitrogen.

Description

Adsorb CO2Preparation method of nitrogen-doped porous carbon material
Technical Field
The invention relates to the field of porous carbon materials, in particular to a method for adsorbing CO2The method for preparing the nitrogen-doped porous carbon material.
Background
The economic development of human society depends on energy, and the combustion of fossil fuels such as coal, oil and natural gas is the main way of energy supply, and a large amount of CO released in the process2Causing global warming, rising sea level, and more serious environmental and ecological problems. Therefore, CO with low development cost, high efficiency and good selectivity2The capture technique is of great significance.
Currently, CO separation and capture2The method of (3) is selected from solvent absorption, membrane separation, chemical and physical adsorption, and cryogenic separation. Among them, the adsorption method has a potential for large-scale application in industrial production due to its characteristics of low cost, low energy consumption, easy operation, etc. Common adsorbents include molecular sieves, amine-functionalized organic polymers, graphene-based materials, porous carbon materials, and the like. Wherein the porous carbon material has the characteristics of large specific surface area, developed pore structure, stable performance, low cost, easy surface modification, rapid regeneration and the like, so that the porous carbon material can be used for CO2The adsorption field has great application prospect. Porous carbon material to CO2The adsorption can be divided into chemical adsorption and physical adsorption, wherein the former mainly utilizes nitrogen-containing functional groups and CO2Interacting with each other to generate chemical reaction and generate chemical adsorption, wherein the chemical adsorption is realized by utilizing ultramicropores (the pore diameter is less than or equal to 1 nm) of the carbon material to perform CO2By the two aspects of the physical adsorption of (A) and (B), CO is realized2Efficient capture. Therefore, the preparation of the porous carbon material with high nitrogen content, more ultramicropores (the pore diameter is less than or equal to 1 nm) and large pore volume is a clear target.
The preparation method of the porous carbon material is divided into a chemical activation method and a physical activation method. CN103157436A reports an adsorption of CO2The preparation method of the pine nut shell-based activated carbon comprises the steps of carbonizing pine nut powder at 500 ℃, soaking the carbonized pine nut powder in KOH solution for 48 hours, and then carrying out chemical activation treatment at 500-900 ℃, wherein the specific surface area can reach 966-1944 m2However, due to poor compatibility of the inorganic base and the carbon structure generated by high-temperature activation, the specific surface area of the generated carbon material is large but the active functional groups are few, and the prepared activated carbon has CO resistance2The maximum adsorption amount of (2) is only 5.0 mmol/g, and the average adsorption amount of the sample is 4.0 mmol/g. In addition, after activation, a large amount of high-purity water or hydrochloric acid is required to be repeatedly washed and dried to remove metal cations, and the process is complex, time-consuming and energy-consuming. In order to increase the number of functional groups on the activated carbon structure, the adoption of organic base activation with good compatibility with the carbon structure is a pioneering thought. CN107665777A discloses a method for preparing biomass-based activated carbon material, which adopts organic amine, such as ethylenediamine tetraacetic acid and alkaline compoundAnd (3) impregnating the oxidized biomass raw material with the mixed solution, drying, carbonizing at 500-600 ℃, fixing nitrogen, and activating with diammonium hydrogen phosphate, sodium carbonate and the like at the same temperature range to obtain the activated carbon with excellent adsorption performance.
Physical activation techniques such as CO2Activation, steam activation, and the like have been used in the field of activation of carbon materials in recent years to increase the content of micropores in the porous carbon material. CN106044740A reports a preparation method of a nano porous carbon material, wherein resorcinol and formaldehyde react, and sodium carbonate is used as a catalyst to prepare organic wet gel. In sequence N2And CO2High-temperature treatment in a gas environment to obtain the nano porous carbon with the specific surface area of 2336 m2Activated nanoporous carbon material per gram.
Production of highly active CO from waste materials from an environmental and sustainability point of view2Adsorbents will be of more interest. Adsorption 2011, 17: 795, Liying Liu et al reported that waste fly ash was made into A-type and A + X mixed molecular sieves by an alkali fusion method, both catalysts could be regenerated, but the adsorption performance was general due to limited specific surface, with CO at 0 ℃ and 25 ℃2The adsorption amounts were 4.25 mmol/g and 3.75 mmol/g, respectively. Polyurethane foam is an important thermosetting polymer, and contains abundant nitrogen. Since the demand for polyurethane products has increased year by year, a large amount of waste including useless scrap, used polyurethane foam, and the like is generated. From Polymer Engineering&Science 2013, 53(7): 1357 reports that the regeneration of waste polyurethane is time-consuming and labor-consuming, most of the waste polyurethane is directly incinerated, but a large amount of nitrogen oxide and carbon oxide are generated to cause serious environmental pollution. Therefore, it is necessary to develop a path for preparing the high-value nitrogen-rich carbon material from the polyurethane foam waste, so that the waste can be changed into valuable materials, and the environmental pollution can be reduced.
In the prior patent, quaternary ammonium base with rich nitrogen content is not used as an activating agent to be combined with waste polyurethane products to prepare the porous carbon material, and the invention carbonizes and fixes nitrogen for waste polyurethane foam at lower temperature by adopting the quaternary ammonium base, thereby improving the carbon materialThe number of active functional groups is added, the steps of acid washing, drying and the like are omitted, and the operation flow is simplified. With simultaneous binding of CO2Physical activation can obtain abundant ultramicropores, and is helpful for improving CO2The amount of adsorption.
Disclosure of Invention
The invention aims to provide the CO adsorption material which has the advantages of low cost, low energy consumption, no pollution, high adsorption quantity, excellent selectivity and excellent cyclic regeneration performance2The preparation method of the nitrogen-doped porous carbon material adopts organic quaternary ammonium base to replace inorganic base as a chemical activator and combines CO2The physical activation method is used for preparing the porous carbon material with ultramicropores, rich nitrogen content and large specific surface area.
In order to achieve the purpose, the invention provides the following technical scheme:
adsorb CO2The preparation method of the nitrogen-doped porous carbon material comprises the following steps:
(1) crushing the waste polyurethane foam into particles of 2 mm to 5 mm, then placing the particles into a quaternary ammonium base aqueous solution with the mass percent of 25% for dipping treatment for 1 to 10 hours, and after the dipping treatment, carrying out vacuum drying for 10 to 30 hours at the temperature of 50 to 80 ℃;
(2) impregnating a polyurethane foam impregnated with a quaternary ammonium base in N2Carrying out low-temperature chemical activation treatment in the atmosphere;
(3) directly subjecting the activated product to CO without cooling and acid washing2Physical activation, namely obtaining the adsorbed CO with large specific surface area and micropore volume and rich nitrogen content2The porous carbon material is doped with nitrogen.
The quaternary ammonium base in the step (1) is one or more of 25% by mass of aqueous solution of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide mixed in any proportion.
The mass ratio of the polyurethane foam to the quaternary ammonium base aqueous solution in the step (1) is 1: 0.8 to 5.
The dipping treatment in the step (1) is carried out under the conditions of vacuum pumping and magnetic stirring.
The step (2) of activation treatment is in a tube furnaceHeating to 400-600 ℃ at a rate of 3-10 ℃/min and maintaining for 1-3 h, N2The atmosphere means that N is continuously introduced at a rate of 60-120 ml/min2。
CO in step (3)2The physical activation is carried out at 800-1000 ℃, and CO is continuously introduced at the speed of 15-50 ml/min2And (5) gas is used for 1-3 h.
The CO is2Physical activation treatment Process is N2Heating to 800-1000 ℃ at the speed of 5 ℃/min under the atmosphere condition, and introducing formed CO2Keeping the gas at constant temperature for 1-2 h, and immediately switching to N after activation2In N at2The protection is reduced to room temperature.
The adsorption of CO2Doping a porous carbon material with nitrogen, wherein the specific surface area is 847-1560 m2Per g, the volume of the ultra-microporous pores with the pore diameter less than 1 nm is 0.15-0.25 cm3The nitrogen content is 6.84-10.46 wt%.
The preparation method of the nitrogen-doped porous carbon material has the beneficial effects that:
(1) the polyurethane foam is waste with high nitrogen content (8.87 wt%), has huge energy consumption for waste treatment and can cause environmental pollution, and the waste is prepared into nitrogen-doped porous carbon for capturing CO2The thought can change waste into valuable, a large amount of waste polyurethane foam can be generated every year, and the raw material supply can be ensured.
(2) The preparation of nitrogen-doped porous carbon materials by using organic quaternary ammonium base with strong alkalinity as an alkali source to carbonize polyurethane foam at low temperature and fix nitrogen is used by few people so far. The quaternary ammonium base can provide a nitrogen source so that the carbonized product has high nitrogen content; meanwhile, as the quaternary ammonium base does not contain metal cations such as potassium, sodium and the like, acid washing, drying and other procedures are not needed after activation, so that the process flow can be shortened, and the energy consumption and pollution are reduced.
(3) The method combines chemical and physical activation, uses organic quaternary ammonium base as chemical reagent for activation at low temperature, can effectively fix nitrogen to prevent nitrogen loss at high temperature, improves nitrogen content, simultaneously performs pore-forming, and then directly heats to perform CO2Physical activation can produce a large amount of ultramicropores. Due to the close pore diameter of the ultramicroporesCO2Molecular dynamic diameter, thereby effectively increasing CO2The amount of adsorption.
(4) The nitrogen-doped porous carbon material prepared by the method has the advantages of low cost, high adsorption capacity (6.6 mmol/g at 273K) and CO2The adsorption selectivity and the cyclic regeneration performance are excellent, and the adsorbent has great potential to become a commercial adsorbent in the future.
Drawings
FIGS. 1 (a) (b) are respectively CO adsorption according to example 1 of the present invention2Scanning electron microscope and transmission electron microscope photographs of the microscopic morphology of the polyurethane foam-based nitrogen-doped porous carbon material;
FIG. 2 is a diagram of CO adsorption according to example 1 of the present invention2The pore volume of the ultramicropore accumulated (the pore diameter is less than or equal to 1 nm) of the polyurethane foam-based nitrogen-doped porous carbon material is used;
FIG. 3 is an adsorption of CO according to example 1 of the present invention2An X-ray photoelectron energy spectrum of the polyurethane foam-based nitrogen-doped porous carbon material;
FIG. 4 shows CO adsorption according to example 1 of the present invention2Polyurethane foam-based nitrogen-doped porous carbon material at 0 ℃ and 25 ℃ to CO2Adsorption and desorption isotherm diagrams of (1);
FIG. 5 is an adsorption of CO according to example 1 of the present invention2CO-pair by using polyurethane foam-based nitrogen-doped porous carbon material2And N2Adsorption isotherm diagram of (a);
FIG. 6 shows CO adsorption according to example 1 of the present invention2Doping porous carbon material with polyurethane foam-based nitrogen five times of CO continuously2Adsorption cycle regeneration curve.
Detailed Description
The present invention is further described in detail below with reference to examples, which are intended to be illustrative of the present invention and should not be construed as limiting the scope of the present invention to the following examples. A schematic of the example is shown in the drawings.
Example 1:
crushing waste polyurethane foam into particles of 2 mm, taking 10 g, and soaking in 15 g of 25% tetramethyl hydrogen by mass fraction under the condition of vacuumizing and magnetic stirringSoaking in ammonium oxide solution for 2 hr, drying in 55 deg.C vacuum oven for 30 hr, cooling, placing in tube furnace, and continuously introducing N at 80 ml/min2Heating to 500 ℃ at the speed of 5 ℃/min, keeping for 2.5 h, performing chemical activation and fixing nitrogen; followed by direct CO2Physical activation, i.e. raising to 900 ℃ at a rate of 5 ℃/min and adding N2Conversion to CO2Making ultramicropores with pore diameter less than 1 nm, introducing CO2At a rate of 35ml/min for 2 hours, immediately switch to N upon completion of activation2And cooling to room temperature under the protection of the nitrogen-doped porous carbon material to obtain the polyurethane foam-based nitrogen-doped porous carbon material.
As can be seen from FIG. 1a, the surface roughness of the sample after activation by this method forms many macro-pores, and the surface roughness is in CO2After activation a worm-like microporous structure of stacked graphite layers appears (as shown in fig. 1 b). The prepared nitrogen-doped porous carbon has the BET surface area of 1430 m2The pore volume of ultra-microporous (pore diameter less than or equal to 1 nm) can reach 0.21 cm3The content of nitrogen in the porous carbon material is rich as shown in figure 2, and the content of nitrogen is 8.78 wt% through organic element analysis and test, as can be seen from X-ray photoelectron spectroscopy (figure 3).
Use thereof for CO2The adsorption test was carried out on a BEL-SORP-max apparatus, and the samples were degassed at 150 ℃ for 2 hours for pretreatment before adsorption, and the results are shown in FIG. 4, with CO at 0 ℃2The adsorption capacity can reach 6.6 mmol/g, and the adsorption capacity at 25 ℃ is 4.4 mmol/g; adsorption of CO in the examples of the invention2The polyurethane foam-based nitrogen-doped porous carbon is used for CO2Relative to N2The selectivity is 13 (as shown in FIG. 5), which illustrates the use of nitrogen-doped porous carbon of the present invention on flue gas (12% CO) generated by coal combustion in power plants2、80% N2、8% H2CO in O (g)2Has good selective adsorption capacity. After the sample is subjected to an adsorption experiment, vacuumizing to 10 at room temperature-4below bar, a second adsorption experiment was performed immediately, as shown in FIG. 6 for CO2The adsorption amount is hardly reduced after five times of cycle experiments, and the polyurethane foam-based porous carbon material is used for capturing CO2The process shows strong performanceAnd (4) reproducibility.
Example 2:
crushing waste polyurethane foam into particles of 3 mm x 3 mm, taking 10 g, soaking in 25 g of tetraethylammonium hydroxide solution with the mass fraction of 25% under the condition of vacuumizing and magnetic stirring for 4 h, then drying in a vacuum drying oven at 65 ℃ for 25 h, cooling, putting into a tube furnace, and continuously introducing N at the speed of 100 ml/min2Heating to 600 ℃ at the speed of 8 ℃/min, keeping for 2 h for chemical activation and nitrogen fixation; followed by direct CO2Physical activation, i.e. raising to 800 ℃ at a rate of 5 ℃/min and adding N2Conversion to CO2Making ultramicropores with pore diameter less than 1 nm, introducing CO2At a rate of 25ml/min for 2 hours, immediately switch to N upon completion of activation2And cooling to room temperature under the protection of the nitrogen-doped porous carbon material to obtain the polyurethane foam-based nitrogen-doped porous carbon material. The BET specific surface area is 1247 m2G, ultra-microporous (pore diameter less than or equal to 1 nm) pore volume of 0.18 cm3The nitrogen content is 9.23 wt%, and the scanning and projection electron micrograph of the product has the characteristics of figure 1, the ultra-microporous cumulative pore volume has the characteristics of figure 2, and the X-ray photoelectron spectrum has the characteristics of figure 3.
The prepared nitrogen-doped porous carbon material is used for CO2The adsorption test evaluation was similar to example 1. CO at 0 ℃ and 25 ℃2The adsorption amounts were 5.88 mmol/g and 3.85 mmol/g, respectively. The nitrogen-doped porous carbon material of the embodiment of the invention is used for treating CO2Relative to N2The selectivity of (A) was 12.5. In addition, five carbon dioxide cycle regeneration experiments were performed, and the results have the characteristics of fig. 6, showing good regenerability.
Example 3:
crushing waste polyurethane foam into 4 mm particles, taking 10 g, soaking in 8 g of tetrapropylammonium hydroxide solution with the mass fraction of 25% under the condition of vacuumizing and magnetic stirring, soaking for 6 h, then drying for 20 h in a vacuum drying oven at the temperature of 75 ℃, cooling, putting into a tube furnace, and continuously introducing N at the speed of 90 ml/min2Heating to 500 ℃ at the speed of 5 ℃/min, keeping for 2.5 h, performing chemical activation and fixing nitrogen; followed by direct CO2The physical activation is carried out on the raw materials,i.e. raising the temperature to 1000 ℃ at a rate of 5 ℃/min and adding N2Conversion to CO2Making ultramicropores with pore diameter less than 1 nm, introducing CO2At a rate of 35ml/min and for 1.5 h, switch to N immediately after activation is complete2And cooling to room temperature under the protection of the nitrogen-doped porous carbon material to obtain the polyurethane foam-based nitrogen-doped porous carbon material. The BET specific surface area is 1510 m2G, ultra-microporous (pore diameter less than or equal to 1 nm) pore volume of 0.19 cm3The nitrogen content is 7.12 wt%, and the scanning and projection electron micrograph of the product has the characteristics of figure 1, the ultra-microporous cumulative pore volume has the characteristics of figure 2, and the X-ray photoelectron spectrum has the characteristics of figure 3.
The prepared nitrogen-doped porous carbon material is used for CO2The adsorption test evaluation was similar to example 1. CO at 0 ℃ and 25 ℃2The adsorption amounts were 6.08 mmol/g and 4.07 mmol/g, respectively. The nitrogen-doped porous carbon material of the embodiment of the invention is used for treating CO2Relative to N2The selectivity of (A) was 12.7. In addition, five carbon dioxide cycle regeneration experiments were performed, and the results have the characteristics of fig. 6, showing good regenerability.
Example 4:
crushing waste polyurethane foam into 5 mm by 5 mm particles, taking 10 g of the waste polyurethane foam, soaking the waste polyurethane foam in 50 g of tetrabutylammonium hydroxide solution with the mass fraction of 25% under the condition of vacuumizing and magnetic stirring for 8 hours, then drying the waste polyurethane foam in a vacuum drying oven at 65 ℃ for 25 hours, cooling the waste polyurethane foam, putting the waste polyurethane foam into a tube furnace, and continuously introducing N at the speed of 75 ml/min2Heating to 400 ℃ at the speed of 3 ℃/min, keeping for 3 h, performing chemical activation and fixing nitrogen; followed by direct CO2Physical activation, i.e. raising to 800 ℃ at a rate of 5 ℃/min and adding N2Conversion to CO2Making ultramicropores with pore diameter less than 1 nm, introducing CO2At a rate of 20 ml/min for 2 hours, immediately switch to N upon completion of activation2And cooling to room temperature under the protection of the nitrogen-doped porous carbon material to obtain the polyurethane foam-based nitrogen-doped porous carbon material. The BET specific surface area is 847 m2G, ultra-microporous (pore diameter less than or equal to 1 nm) pore volume of 0.17 cm3The nitrogen content is 10.46 wt%, the scanning and projection electron micrograph of the product has the characteristics of figure 1, and the ultra-microporous cumulative pore volume has the characteristics of figure 2The X-ray photoelectron spectrum has the characteristics of fig. 3.
The prepared nitrogen-doped porous carbon material is used for CO2The adsorption test evaluation was similar to example 1. CO at 0 ℃ and 25 ℃2The adsorption amounts were 5.44 mmol/g and 3.64 mmol/g, respectively. The nitrogen-doped porous carbon material of the embodiment of the invention is used for treating CO2Relative to N2The selectivity of (A) was 12.5. In addition, five carbon dioxide cycle regeneration experiments were performed, and the results have the characteristics of fig. 6, showing good regenerability.
Example 5:
crushing waste polyurethane foam into particles of 4 mm, taking 10 g, soaking in a mixed solution of 15 g of 25% tetramethylammonium hydroxide and 10 g of tetrapropylammonium hydroxide under the condition of vacuumizing and magnetic stirring, soaking for 4 h, then drying in a vacuum drying oven at 80 ℃ for 10 h, cooling, putting into a tube furnace, and continuously introducing N at the speed of 90 ml/min2Heating to 600 ℃ at the speed of 8 ℃/min, keeping for 1.5 h, performing chemical activation and fixing nitrogen; followed by direct CO2Physical activation, i.e. raising to 1000 ℃ at a rate of 5 ℃/min and adding N2Conversion to CO2Making ultramicropores with pore diameter less than 1 nm, introducing CO2At a rate of 25ml/min and for 1 h, switch to N immediately after activation is complete2And cooling to room temperature under the protection of the nitrogen-doped porous carbon material to obtain the polyurethane foam-based nitrogen-doped porous carbon material. Its BET specific surface area is 1560 m2G, ultra-microporous (pore diameter less than or equal to 1 nm) pore volume of 0.15 cm3The nitrogen content is 6.85 wt%, and the scanning and projection electron micrograph of the product has the characteristics of figure 1, the ultra-microporous cumulative pore volume has the characteristics of figure 2, and the X-ray photoelectron spectrum has the characteristics of figure 3.
The prepared nitrogen-doped porous carbon material is used for CO2The adsorption test evaluation was similar to example 1. CO at 0 ℃ and 25 ℃2The adsorption amounts were 4.95 mmol/g and 3.47 mmol/g, respectively. The nitrogen-doped porous carbon material of the embodiment of the invention is used for treating CO2Relative to N2The selectivity of (2) is 13. In addition, five carbon dioxide cycle regeneration experiments were performed, and the results have the characteristics of fig. 6, showing good regenerability.

Claims (6)

1. Adsorb CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: the method comprises the following steps:
(1) crushing the waste polyurethane foam into particles of 2 mm to 5 mm, then placing the particles into a quaternary ammonium base aqueous solution with the mass percent of 25% for dipping treatment for 1 to 10 hours, and after the dipping treatment, carrying out vacuum drying for 10 to 30 hours at the temperature of 50 to 80 ℃;
(2) impregnating a polyurethane foam impregnated with a quaternary ammonium base in N2Performing low-temperature chemical activation treatment in an atmosphere, wherein the activation treatment is to heat the mixture to 400-600 ℃ at a rate of 3-10 ℃/min in a tube furnace and keep the temperature for 1-3 h, N2The atmosphere means that N is continuously introduced at a rate of 60-120 ml/min2；
(3) Directly subjecting the activated product to CO without cooling and acid washing2Physical activation, namely obtaining the adsorbed CO with large specific surface area and micropore volume and rich nitrogen content2Doping porous carbon materials with nitrogen, CO2The physical activation is that CO is continuously introduced at the speed of 15-50 ml/min at the temperature of 800-1000 DEG C2And (5) gas is used for 1-3 h.
2. The method of claim 1 for adsorbing CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: the quaternary ammonium base in the step (1) is one or more of 25% by mass of aqueous solution of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide mixed in any proportion.
3. The method of claim 1 for adsorbing CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: the mass ratio of the polyurethane foam to the quaternary ammonium base aqueous solution in the step (1) is 1: 0.8 to 5.
4. The method of claim 1 for adsorbing CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: step (1) dipping treatment in vacuum pumpingAnd is carried out under the condition of magnetic stirring.
5. The method of claim 1 for adsorbing CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: the CO is2Physical activation treatment Process is N2Heating to 800-1000 ℃ at the speed of 5 ℃/min under the atmosphere condition, and introducing formed CO2Keeping the gas at constant temperature for 1-2 h, and immediately switching to N after activation2In N at2The protection is reduced to room temperature.
6. The method of claim 5, wherein the adsorbed CO is CO2The preparation method of the nitrogen-doped porous carbon material is characterized by comprising the following steps: the adsorption of CO2Doping a porous carbon material with nitrogen, wherein the specific surface area is 847-1560 m2Per g, the volume of the ultra-microporous pores with the pore diameter less than 1 nm is 0.15-0.25 cm3The nitrogen content is 6.84-10.46 wt%.
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