CN103877932A - Nitrogen-containing carbon materials with good carbon dioxide adsorption separating performances and application thereof - Google Patents

Nitrogen-containing carbon materials with good carbon dioxide adsorption separating performances and application thereof Download PDF

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CN103877932A
CN103877932A CN201210562808.XA CN201210562808A CN103877932A CN 103877932 A CN103877932 A CN 103877932A CN 201210562808 A CN201210562808 A CN 201210562808A CN 103877932 A CN103877932 A CN 103877932A
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carbon
carbon materials
carbon dioxide
nitrogen
materials
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CN103877932B (en
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孙立贤
***
徐芬
张箭
刘双
张焕芝
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to a preparation method of nitrogen-containing carbon materials and carbon dioxide adsorption separating performances of the nitrogen-containing carbon materials, to be more specific, porous carbon materials with different nitrogen contents are prepared by polymerization of a nitrogen-containing compound on activated carbon surface and then calcination, and the porous carbon materials have good carbon dioxide adsorption separating performances. The preparation steps are as follows: ultrasonic dispersion of activated carbon and pyrrole in deionized water, 4 to 10 hours of reaction of the mixed solution at the temperature of 20-80 DEG C by using ammonium sulfate as a catalyst, then filtration, washing, drying, and 1-5 hours of calcination under the protection of a gas at 400-800 DEG C to obtain the nitrogen-containing carbon materials. The preparation method has the advantages of simple preparation process and low cost, nitrogen element can be effectively doped in the activated carbon, and the prepared carbon materials have good carbon dioxide adsorption separating performances.

Description

There is nitrogenous Carbon Materials and the application thereof of good carbon dioxide adsorption separation performance
Technical field
The present invention relates to a kind of preparation method of nitrogenous Carbon Materials and the adsorbing separation to carbon dioxide, specifically be to prepare the porous carbon material of different nitrogen contents by changing synthesis condition, and there is good carbon dioxide adsorption separation performance.
Background technology
Due to the excessive use of fossil fuel, before the concentration ratio industrial revolution of atmosphere percent of greenhouse gases carbon dioxide, increase by 30% left and right, cause serious environmental pollution and greenhouse effects.CO can be effectively caught in searching 2method become the task of top priority.Mainly comprise following a few class for the technology of carbon dioxide absorption at present: solution absorption, cryogenic absorption, film separates adsorption technology and solid dielectric adsorption technology.Industrial extensive use be the adsorption from aqueous solution technology of amine, also there is fatal shortcoming although this method can effectively be caught carbon dioxide: corrosivity is high, and cost is high, volatile and degraded, adsorbent reactivation consumes energy very much.Porous carbon material has bigger serface and high porosity, can be for to CO 2absorption.But Carbon Materials is to CO 2/ N 2selective absorption coefficient not high, therefore having limited this type of material can only use being rich in carbon dioxide atmosphere.In order to improve Carbon Materials to carbon dioxide adsorbing separation ability, the research of material being carried out to the load of N nitrogen is subject to paying close attention to more and more widely.
It is raw material that Wei etc. utilize the dregs of beans of rich Nitrogen element, is activated and is prepared porous activated carbon (Xing W, Liu C, Zhou Z, Zhang L, Zhou J, Zhuo S, et al.Energy & Environmental Science.2012 by KOH; 5 (6): 7323.), at 1atm and 25 DEG C, CO 2adsorbance reach 4.24mmol/L.Research shows, CO 2adsorbance with have direct relation containing N amount.Sevilla etc. are synthetic polypyrrole taking pyridine as raw material, then by preparing nitrogenous Carbon Materials (Sevilla M, Valle-Vig ó n P, Fuertes A B.Advanced Functional Materials.2011 with KOH activation; 21 (14): 2781-2787.), at 1atm and 25 DEG C, CO 2adsorbance reach 3.9mmol/L.Research shows, CO 2adsorbance and nitrogen content have direct relation.Research shows, doping nitrogen element can improve material to CO 2/ N 2selective absorption performance.
Taking active carbon as charcoal source, in order to improve the nitrogen content in Carbon Materials, we are by polymerization, the method of calcining is prepared a series of porous carbon materials, taking pyrroles as nitrogenous source, can obtain the Carbon Materials of different nitrogen contents by controlling reaction condition, and study the adsorption separation performance of material to carbon dioxide.
Summary of the invention
The present invention relates to a kind of preparation method of nitrogenous Carbon Materials and the adsorbing separation to carbon dioxide, specifically be to prepare the porous carbon material of different nitrogen contents by changing synthesis condition, and there is good carbon dioxide adsorption separation performance.
For achieving the above object, the technical solution used in the present invention is as follows:
Nitrogenous Carbon Materials, can prepare as follows,
1) active carbon and pyrroles are dissolved in to deionized water (adding 1～10g active carbon and 1～20g pyrroles in every 100mL deionized water), add again 2-10g ammonium persulfate, reaction temperature is 20-80 DEG C, and the reaction time is 4～10 hours, naturally cools to room temperature.
2), by collection of products, suction filtration, washing, 50～100 DEG C of vacuum drying, make carbon precursor.
3) presoma is calcined to 1-5 hour under gas shield under 400～800 DEG C of conditions, cooling after, washing, dry, obtain having good carbon dioxide adsorption separation performance containing nitride polyporous material.
The preparation method of described step 1) Carbon Materials is catalytic polymerization, wherein active carbon and pyrroles (0.5～2) interpolation in mass ratio; Synthesis temperature is 20～80 DEG C; Generated time is 4～10 hours.
Described step 2) baking temperature is 50～100 DEG C; Operating time is adjustable at 10～24 hours;
Prepare the compound of active carbon and polypyrrole by the method for polymerization, prepare nitrogenous Carbon Materials by the method for high-temperature calcination.Can control the nitrogen content of Carbon Materials by controlling synthesis condition.
Under 273K, carbon dioxide is had to good adsorbing separation effect.
Described nitrogenous Carbon Materials is carried out to the test of carbon dioxide adsorption separation performance, and specific operation process is:
1) take 0.1g left and right sample, under vacuum condition at 200 DEG C, degassed 12h, the cooling rear sample quality that accurately takes.
2) put into instrument after taking sample quality, select the absorption program of carbon dioxide at 273K, by computer monitor Carbon Materials adsorption and desorption situation to carbon dioxide under different relative pressures.Then calculate Carbon Materials to CO by calculating 2/ N 2adsorbing separation coefficient.
3) put into instrument after taking sample quality, select the absorption program of nitrogen at 273K, by computer monitor Carbon Materials adsorption and desorption situation to nitrogen under different relative pressures.
Carbon Materials provided by the present invention and preparation method's tool have the following advantages:
1. synthetic simple, cost is lower.Adopt catalytic polymerization, can obtain at short notice having the product of higher yields.
2. can prepare the Carbon Materials of different nitrogen contents by controlling synthesis condition.Same reactant, can obtain different nitrogen contents, the Carbon Materials of different specific areas by the condition such as ratio, calcining heat that changes reactant.
3. Carbon Materials has reversible adsorption and desorption carbon dioxide under 273K, can do the sorbing material of carbon dioxide.
4. Carbon Materials adsorbance to nitrogen under 273K is lower, can do the parting material of carbon dioxide.
Brief description of the drawings
Fig. 1 is that the AC-PPy-600 Carbon Materials of specific embodiments of the invention 1 is at the nitrogen adsorption of 77K, desorption schematic diagram;
Fig. 2 is the aperture structure distribution schematic diagram of the AC-PPy-600 Carbon Materials of specific embodiments of the invention 1.
Fig. 3 is the schematic diagram of the AC-PPy-600 Carbon Materials infrared spectrum of specific embodiments of the invention 1.
Fig. 4 be the Carbon Materials of AC-PPy-600 of specific embodiments of the invention 1 at 273K to carbon dioxide adsorption and desorption schematic diagram.
Fig. 5 be the Carbon Materials of AC-PPy-600 of specific embodiments of the invention 1 at 273K to nitrogen adsorption, desorption schematic diagram.
Fig. 6 is that the AC-PPy-600 Carbon Materials of specific embodiments of the invention 1 is at the nitrogen adsorption of 77K, desorption schematic diagram;
Fig. 7 is the aperture structure distribution schematic diagram of the AC-PPy-600 Carbon Materials of specific embodiments of the invention 1.
Fig. 8 is the schematic diagram of the AC-PPy-600 Carbon Materials infrared spectrum of specific embodiments of the invention 1.
Fig. 9 be the Carbon Materials of AC-PPy-600 of specific embodiments of the invention 1 at 273K to carbon dioxide adsorption and desorption schematic diagram.
Figure 10 be the Carbon Materials of AC-PPy-600 of specific embodiments of the invention 1 at 273K to nitrogen adsorption, desorption schematic diagram.
Detailed description of the invention
Carbon dioxide absorption property test to described Carbon Materials is carried out on Quantachrome company physical adsorption appearance (Autosorb-1sorptometer), and specific operation process is:
1) take 0.1g left and right sample, under vacuum condition at 200 DEG C, degassed 12h, the cooling rear sample quality that accurately takes.
2) put into instrument after taking sample quality, select the absorption program of carbon dioxide at 273K, by computer monitor Carbon Materials adsorption and desorption situation to carbon dioxide under different relative pressures.
The carbon dioxide separation performance test of described Carbon Materials is carried out on Quantachrome company physical adsorption appearance (Autosorb-1sorptometer), and specific operation process is:
1) take 0.1-0.3g left and right sample, under vacuum condition at 200 DEG C, degassed 12h, the cooling rear sample quality that accurately takes.
2) put into instrument after taking sample quality, select carbon dioxide or the nitrogen absorption program at 273K, by computer monitor Carbon Materials adsorption and desorption situation to carbon dioxide or nitrogen under different relative pressures.Then calculate Carbon Materials to CO by calculating 2/ N 2adsorbing separation coefficient.
Embodiment 1
1. active carbon and pyrroles are dissolved in to deionized water (adding 1g active carbon and 1g pyrroles in every 100mL deionized water), then to add 2g ammonium persulfate, reaction temperature be 40 DEG C, the reaction time is 4 hours, naturally cools to room temperature.
2. by collection of products, suction filtration, washing, 80 DEG C of vacuum drying, make carbon precursor.
3. presoma is calcined 2 hours under gas shield under 600 DEG C of conditions, cooling after, washing, dry, obtain having the nitrogenous porous carbon material AC-PPy-600 of good carbon dioxide adsorption separation performance.
Embodiment 2
4. active carbon and pyrroles are dissolved in to deionized water (adding 2g active carbon and 4g pyrroles in every 100mL deionized water), then to add 8g ammonium persulfate, reaction temperature be 4 DEG C, the reaction time is 4 hours, naturally cools to room temperature.
5. by collection of products, suction filtration, washing, 80 DEG C of vacuum drying, make carbon precursor.
6. presoma is calcined 2 hours under gas shield under 600 DEG C of conditions, cooling after, washing, dry, obtain having the nitrogenous porous carbon material AC-2PPy-600 of good carbon dioxide adsorption separation performance.

Claims (5)

1. the nitrogenous Carbon Materials with good carbon dioxide adsorption separation performance, is characterized in that: can prepare as follows:
1) active carbon and pyrroles are dissolved in deionized water, add 1～10g active carbon and 1～20g pyrroles in every 100mL water, then to add 2-10g ammonium persulfate, reaction temperature be 20-80 DEG C, the reaction time is 4～10 hours, naturally cools to room temperature;
2) solid product is collected, suction filtration, deionized water washing, 50～100 DEG C of vacuum drying, makes carbon precursor;
3) presoma is calcined to 1-5 hour under inert gas shielding under 400～800 DEG C of conditions, cooling after, washing, dry, obtain nitrogenous porous carbon material.
2. according to Carbon Materials claimed in claim 1, it is characterized in that:
Described step 1) carbon precursor be prepared as catalyst polymerization, wherein active carbon adds than (0.25～2) by metering with pyrroles.
3. according to Carbon Materials claimed in claim 1, it is characterized in that:
Described step 2) baking temperature is 50～100 DEG C; Operating time is adjustable at 10～24 hours.
4. an application for Carbon Materials described in claim 1, is characterized in that:
Described Carbon Materials is for the carbon dioxide adsorbing separation of gas.
5. according to the application of Carbon Materials described in claim 4, it is characterized in that:
Described gas is carbon dioxide or carbonated gaseous mixture, and in gaseous mixture, remaining gas is H 2, O 2, N 2, one or two or more kinds in CO, carbon dioxide content 0-100% in gaseous mixture.
CN201210562808.XA 2012-12-21 2012-12-21 There is nitrogenous Carbon Materials and the application thereof of good carbon dioxide adsorption separation performance Expired - Fee Related CN103877932B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104148014A (en) * 2014-07-30 2014-11-19 华南理工大学 High-water-absorbing carbon material under low-humidity condition and modification and preparation method thereof
CN104289246A (en) * 2014-10-11 2015-01-21 中国科学院上海高等研究院 Novel mercury-free catalyst and application of mercury-free catalyst in synthesis of vinyl chloride
CN104525257A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Polypyrrole activated carbon catalyst and application thereof in vinyl chloride synthesis
CN106582587A (en) * 2017-02-27 2017-04-26 中国科学院上海高等研究院 Microalgae-based nitrogenous carbon material used for adsorbing carbon dioxide and preparing method thereof
CN107875801A (en) * 2016-09-30 2018-04-06 中国科学院大连化学物理研究所 One kind prepares nitrogen-doped carbon material and its application by precursor of porous polymer with nitrogen
CN108262016A (en) * 2018-03-23 2018-07-10 宁波大学 A kind of method of slag adsorbing and removing carbon dioxide in gas
CN110327905A (en) * 2019-08-07 2019-10-15 中国石油化工股份有限公司 A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base
CN112981147A (en) * 2021-02-08 2021-06-18 中南大学 Capacitive deionization rare earth recovery device and method based on nitrogen-doped activated carbon electrode material

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CN101612554A (en) * 2009-08-13 2009-12-30 沈阳建筑大学 The preparation method of conducting polymer modified active carbon

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104148014A (en) * 2014-07-30 2014-11-19 华南理工大学 High-water-absorbing carbon material under low-humidity condition and modification and preparation method thereof
CN104289246A (en) * 2014-10-11 2015-01-21 中国科学院上海高等研究院 Novel mercury-free catalyst and application of mercury-free catalyst in synthesis of vinyl chloride
CN104525257A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Polypyrrole activated carbon catalyst and application thereof in vinyl chloride synthesis
CN107875801A (en) * 2016-09-30 2018-04-06 中国科学院大连化学物理研究所 One kind prepares nitrogen-doped carbon material and its application by precursor of porous polymer with nitrogen
CN107875801B (en) * 2016-09-30 2020-10-30 中国科学院大连化学物理研究所 Nitrogen-doped carbon material prepared by taking porous nitrogen-containing polymer as precursor and application thereof
CN106582587A (en) * 2017-02-27 2017-04-26 中国科学院上海高等研究院 Microalgae-based nitrogenous carbon material used for adsorbing carbon dioxide and preparing method thereof
CN108262016A (en) * 2018-03-23 2018-07-10 宁波大学 A kind of method of slag adsorbing and removing carbon dioxide in gas
CN110327905A (en) * 2019-08-07 2019-10-15 中国石油化工股份有限公司 A kind of nitrogenous porous carbon nano-composite material preparation method of polyaniline carbon nanotube base
CN112981147A (en) * 2021-02-08 2021-06-18 中南大学 Capacitive deionization rare earth recovery device and method based on nitrogen-doped activated carbon electrode material

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