CN104310396A - Preparation method of activated carbon with capability of efficiently adsorbing CO2 - Google Patents
Preparation method of activated carbon with capability of efficiently adsorbing CO2 Download PDFInfo
- Publication number
- CN104310396A CN104310396A CN201410560606.0A CN201410560606A CN104310396A CN 104310396 A CN104310396 A CN 104310396A CN 201410560606 A CN201410560606 A CN 201410560606A CN 104310396 A CN104310396 A CN 104310396A
- Authority
- CN
- China
- Prior art keywords
- nitrogenous
- prepolymer
- preparation
- temperature
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of activated carbon with capability of efficiently adsorbing CO2. The preparation method comprises the following steps: adding p-aminophenol after reaction of melamine and formaldehyde, carrying out reflux reaction for 4-8h, cooling until room temperature, then adding a methanol solution of F127 or P123, respectively segmenting at temperatures of 100-120 DEG C, 130-160 DEG C, 170-190 DEG C, 210-230 DEG C and 240-260 DEG C, respectively curing to obtain nitrogen-containing prepolymer, then carbonizing, mixing a carbonized material and KOH, activating for 0.5-2.0h, repeatedly washing by deionized water until neutrality finally, and drying to obtain the product. The activated carbon has the advantages of high specific surface area, high nitrogen content and high CO2 adsorption performance.
Description
Technical field
The present invention relates to a kind of preparation method of gac, relate in particular to a kind of efficient adsorption CO
2the preparation method of gac.
Background technology
Along with going from bad to worse of the environmental problems such as global warming, conventional fossil fuel burning produces a large amount of greenhouse gases CO
2catch the concern being subject to people with Plugging Technology Applied gradually.Except the methods such as traditional liquefied ammonia absorption process, membrane sepn, low-temperature distillation, active carbon adsorption relies on the advantage such as its cheap cost, high-adsorption-capacity, high Selective adsorption, excellent cyclic regeneration stability in use, is current CO
2one of technology most with prospects in the numerous technology of gas entrapment.Although common commercial gac has higher specific surface area, flourishing microvoid structure and large pore volume, be directly used in CO
2still there is more problem in catching of gas, as lower in loading capacity, poor selectivity, adsorption rate are slow, cyclic regeneration life cycle is long.By modes such as modification or graftings at gac table phase or the body alkaline nitrogen-containing functional group of middle introducing mutually, effectively can improve gac to the loading capacity of acid CO2 gas and adsorption selectivity, thus receive and pay close attention to widely.
Number of patent application is that " having nitrogenous Carbon Materials and the application thereof of good carbon dioxide adsorption separation performance " patent of 201210562808.X is by being polymerized a kind of nitrogenous compound at activated carbon surface, obtain the porous carbon material with different nitrogen contents again through calcining, can be used for CO in multiple gases
2fractionation by adsorption.Patent does not provide corresponding CO
2separation factor, what was certain was that owing to being polymerized polymer at activated carbon surface, its specific surface area will significantly decline, although can improve CO
2separation factor, but its absorption is significantly declined;
Number of patent application be 201210167846.5 " one catches CO in flue gas
2sorbent material and preparation method thereof " patent have employed porous carbon material dipping equally containing nitrogen compound, carries out drying acquisition afterwards to CO in hydrogen atmosphere
2the trapping agent that loading capacity reaches, the specific surface area of its Carbon Materials used is greater than 800m
2/ g, but do not provide its CO
2catch quantity;
Number of patent application be 201110329392.2 " for catching CO
2the preparation method of spheric active carbon " provide a kind of low cost, high nitrogenous for catching CO
2the preparation method of spheric active carbon.Its nitrogen content is between 1.8-5.4wt%, and CO2 quantity of the catch is between 7.4-14.8wt%;
Number of patent application be 201110329424.9 " a kind of resin carbon specific surface area that improves is beneficial to CO
2the method of catching " in, although the specific surface area of resin carbon is the highest reach 1510m
2/ g, but to CO
2quantity of the catch be only 11.8wt%.
Although above-mentioned patent adopts nitrogenous reagent process finished product gac, or directly adopt polymer with nitrogen to carry out carbonizing, activate and synthesize nitrogenous porous carbon material, but shortcoming that ubiquity Carbon Materials specific surface area is little, nitrogen content is low and yield is lower etc., is difficult to meet efficient capture CO
2requirement.
Summary of the invention
The object of this invention is to provide a kind of high-specific surface area, high nitrogen-containing and high CO
2the preparation method of the gac of absorption property.
Preparation method of the present invention comprises the steps:
(1) synthesis of nitrogenous prepolymer: trimeric cyanamide and formaldehyde add p-aminophenol after stirring reaction 30-90min at 60-90 DEG C, back flow reaction 4-8h at 60-120 DEG C afterwards, cool to room temperature, then the methanol solution of F127 or P123 is added, after stirred at ambient temperature 3-6h, pouring in open container methyl alcohol under room temperature into volatilizees after 8-12h naturally, with the temperature rise rate of 0.5-2 DEG C/min respectively at 100-120,130-160,170-190,210-230 and 240-260 DEG C segmentation solidify 3-6h respectively, obtain nitrogenous prepolymer;
P-aminophenol as above: trimeric cyanamide: formaldehyde mole ratio is 1:(0.5-2): (3-12); The mole number ratio of trimeric cyanamide: F127 or P123 is 1:(0.005-0.02); The methyl alcohol of 20-200ml is added in every mole of amino-phenol;
(2) charing of nitrogenous prepolymer: by nitrogenous prepolymer under nitrogen protection with the ramp of 0.5-2 DEG C/min to 500-700 DEG C, and carbonize 2-4h at this temperature, obtain carbonized material;
(3) activation of nitrogenous prepolymer: by the carbonized material obtained and KOH 1:(1-4 in mass ratio) mix after, with the ramp of 2-5 DEG C/min to 500-700 DEG C, and activate 0.5-2.0h at this temperature, finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
Tool of the present invention has the following advantages:
1, the compound that have employed nitrogen content high due to this patent is polymerized, therefore also containing high nitrogen content in gained prepolymer; Equally, owing to adopting lower charing and activation temperature, also ensure that the nitrogen content in the finished product.
2, this patent have employed the method for chemical activation, and the specific surface area of products obtained therefrom is apparently higher than the performance of conventional physical activation products obtained therefrom.
3, the CO2 absorption property of this patent products obtained therefrom is up to 19.8%.
Embodiment
Embodiment 1
0.5 mol trimeric cyanamide and 3.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 90 min at 60 DEG C, back flow reaction 4h at 100 DEG C afterwards, cool to room temperature, then methanol solution 20 ml of 0.010 mol F127 is added, after stirred at ambient temperature 5h, pouring in open container methyl alcohol under room temperature into volatilizees after 8h naturally, be placed in baking oven with the temperature rise rate of 0.5 DEG C/min respectively at 100,130,170,210 and 240 DEG C segmentation solidify 6h respectively, obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 4h with at the ramp to 500 of 0.5 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:3 mixes in mass ratio with KOH, with the ramp to 500 of 2 DEG C/min DEG C activation 2.0h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1520 m
2/ g, nitrogen content are 8.6 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 15.4 wt%.
Embodiment 2
1.0 mol trimeric cyanamides and 5.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 80 min at 70 DEG C, back flow reaction 5h at 120 DEG C afterwards, cool to room temperature, then methanol solution 80 ml of 0.005 mol F127 is added, after stirred at ambient temperature 3h, pouring in open container methyl alcohol under room temperature into volatilizees after 10h naturally, to be placed in baking oven with the temperature rise rate of 1.0 DEG C/min stage curing 4h at 110,140,180,220 and 250 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 4h with at the ramp to 600 of 0.5 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:1 mixes in mass ratio with KOH, with the ramp to 700 of 5 DEG C/min DEG C activation 0.5h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1550 m
2/ g, nitrogen content are 6.7 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 15.1 wt%.
Embodiment 3
2.0 mol trimeric cyanamides and 12.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 30 min at 80 DEG C, back flow reaction 6h at 60 DEG C afterwards, cool to room temperature, then methanol solution 160 ml of 0.020 mol F127 is added, after stirred at ambient temperature 4h, pouring in open container methyl alcohol under room temperature into volatilizees after 8h naturally, to be placed in baking oven with the temperature rise rate of 2.0 DEG C/min stage curing 2h at 100,150,190,230 and 260 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 3h with at the ramp to 700 of 0.5 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:2 mixes in mass ratio with KOH, with the ramp to 600 of 3 DEG C/min DEG C activation 1.0h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1600 m
2/ g, nitrogen content are 7.8 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 18.1 wt%.
Embodiment 4
1.5 mol trimeric cyanamides and 8.0 mol formaldehyde add 2.0 mol p-aminophenol after stirring reaction 70 min at 90 DEG C, back flow reaction 8h at 100 DEG C afterwards, cool to room temperature, then methanol solution 200 ml of 0.020 mol F127 is added, after stirred at ambient temperature 6h, pouring in open container methyl alcohol under room temperature into volatilizees after 8h naturally, to be placed in baking oven with the temperature rise rate of 1.5 DEG C/min stage curing 4h at 120,140,170,210 and 240 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 4h with at the ramp to 500 of 0.5 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:4 mixes in mass ratio with KOH, with the ramp to 500 of 4 DEG C/min DEG C activation 1.0h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1635 m
2/ g, nitrogen content are 8.2 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 19.8 wt%.
Embodiment 5
0.5 mol trimeric cyanamide and 12.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 80 min at 70 DEG C, back flow reaction 4h at 60 DEG C afterwards, cool to room temperature, then methanol solution 140 ml of 0.016 mol P123 is added, after stirred at ambient temperature 5h, pouring in open container methyl alcohol under room temperature into volatilizees after 8h naturally, to be placed in baking oven with the temperature rise rate of 0.5 DEG C/min stage curing 6h at 110,130,170,220 and 250 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 4h with at the ramp to 700 of 0.5 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:3 mixes in mass ratio with KOH, with the ramp to 700 of 3 DEG C/min DEG C activation 1.5h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1842 m
2/ g, nitrogen content are 5.8 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 15.6 wt%.
Embodiment 6
1.5 mol trimeric cyanamides and 9.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 30 min at 90 DEG C, back flow reaction 4h at 110 DEG C afterwards, cool to room temperature, then methanol solution 90 ml of 0.020 mol P123 is added, after stirred at ambient temperature 3h, pouring in open container methyl alcohol under room temperature into volatilizees after 8h naturally, to be placed in baking oven with the temperature rise rate of 1.5 DEG C/min stage curing 5h at 120,150,180,210 and 240 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 3h with at the ramp to 600 of 1.0 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:2 mixes in mass ratio with KOH, with the ramp to 600 of 2 DEG C/min DEG C activation 0.5h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 1930 m
2/ g, nitrogen content are 7.7 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 17.7 wt%.
Embodiment 7
2.0 mol trimeric cyanamides and 3.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 60 min at 70 DEG C, back flow reaction 8h at 80 DEG C afterwards, cool to room temperature, then methanol solution 120 ml of 0.018 mol P123 is added, after stirred at ambient temperature 3h, pouring in open container methyl alcohol under room temperature into volatilizees after 12h naturally, to be placed in baking oven with the temperature rise rate of 2.0 DEG C/min stage curing 3h at 100,140,180,230 and 250 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 2h with at the ramp to 700 of 2 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:1 mixes in mass ratio with KOH, with the ramp to 500 of 4 DEG C/min DEG C activation 2.0h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 2090 m
2/ g, nitrogen content are 8.2 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 18.9 wt%.
Embodiment 8
1.0 mol trimeric cyanamides and 6.0 mol formaldehyde add 1.0 mol p-aminophenol after stirring reaction 90 min at 70 DEG C, back flow reaction 5h at 120 DEG C afterwards, cool to room temperature, then the methanol solution 100ml of 0.018 mol P123 is added, after stirred at ambient temperature 6h, pouring in open container methyl alcohol under room temperature into volatilizees after 10h naturally, to be placed in baking oven with the temperature rise rate of 1.0 DEG C/min stage curing 3h at 110,160,190,230 and 260 DEG C respectively, to obtain nitrogenous prepolymer; Nitrogenous prepolymer is carbonized 2h with at the ramp to 500 of 2 DEG C/min DEG C under nitrogen protection, obtains carbonized material; After by the carbonized material that obtains, 1:1 mixes in mass ratio with KOH, with the ramp to 700 of 5 DEG C/min DEG C activation 0.5h.Finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
The specific surface area of products obtained therefrom is 2180 m
2/ g, nitrogen content are 6.0 wt%, CO
2under 25 DEG C of normal pressures, adsorptive capacity reaches 19.2 wt%.
Claims (2)
1. an efficient adsorption CO
2the preparation method of gac, it is characterized in that comprising the steps:
(1) synthesis of nitrogenous prepolymer: trimeric cyanamide and formaldehyde add p-aminophenol after stirring reaction 30-90min at 60-90 DEG C, back flow reaction 4-8h at 60-120 DEG C afterwards, cool to room temperature, then the methanol solution of F127 or P123 is added, after stirred at ambient temperature 3-6h, pouring in open container methyl alcohol under room temperature into volatilizees after 8-12h naturally, with the temperature rise rate of 0.5-2 DEG C/min respectively at 100-120,130-160,170-190,210-230 and 240-260 DEG C segmentation solidify 3-6h respectively, obtain nitrogenous prepolymer;
(2) charing of nitrogenous prepolymer: by nitrogenous prepolymer under nitrogen protection with the ramp of 0.5-2 DEG C/min to 500-700 DEG C, and carbonize 2-4h at this temperature, obtain carbonized material;
(3) activation of nitrogenous prepolymer: after 1:1-4 mixes in mass ratio by the carbonized material and the KOH that obtain, with the ramp of 2-5 DEG C/min to 500-700 DEG C, and activate 0.5-2.0h at this temperature, finally by deionized water repetitive scrubbing to neutral, after drying, obtain product.
2. a kind of efficient adsorption CO as claimed in claim 1
2the preparation method of gac, it is characterized in that described p-aminophenol: trimeric cyanamide: formaldehyde mole ratio is 1:0.5-2:3-12; The mole number ratio of trimeric cyanamide: F127 or P123 is 1:0.005-0.02; The methyl alcohol of 20-200ml is added in every mole of amino-phenol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410560606.0A CN104310396B (en) | 2014-10-21 | 2014-10-21 | A kind of efficient adsorption CO 2the preparation method of gac |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410560606.0A CN104310396B (en) | 2014-10-21 | 2014-10-21 | A kind of efficient adsorption CO 2the preparation method of gac |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104310396A true CN104310396A (en) | 2015-01-28 |
CN104310396B CN104310396B (en) | 2016-04-20 |
Family
ID=52365750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410560606.0A Active CN104310396B (en) | 2014-10-21 | 2014-10-21 | A kind of efficient adsorption CO 2the preparation method of gac |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104310396B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105664850A (en) * | 2016-01-26 | 2016-06-15 | 中国科学院上海高等研究院 | Preparation method and application of high-performance carbon-based carbon dioxide adsorbing material |
CN108529588A (en) * | 2018-03-06 | 2018-09-14 | 河南工程学院 | The preparation method of ordered mesoporous carbon |
CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58213613A (en) * | 1982-06-03 | 1983-12-12 | Sumitomo Bakelite Co Ltd | Preparation of spherical active carbon |
CN102502624A (en) * | 2011-10-22 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Preparation method for acquiring spherical activated carbon of carbon dioxide |
CN102553641A (en) * | 2010-12-08 | 2012-07-11 | 中国中化股份有限公司 | Preparation method for nitrogen-containing activated carbon catalyst |
-
2014
- 2014-10-21 CN CN201410560606.0A patent/CN104310396B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58213613A (en) * | 1982-06-03 | 1983-12-12 | Sumitomo Bakelite Co Ltd | Preparation of spherical active carbon |
CN102553641A (en) * | 2010-12-08 | 2012-07-11 | 中国中化股份有限公司 | Preparation method for nitrogen-containing activated carbon catalyst |
CN102502624A (en) * | 2011-10-22 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Preparation method for acquiring spherical activated carbon of carbon dioxide |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105664850A (en) * | 2016-01-26 | 2016-06-15 | 中国科学院上海高等研究院 | Preparation method and application of high-performance carbon-based carbon dioxide adsorbing material |
CN105664850B (en) * | 2016-01-26 | 2018-06-26 | 中国科学院上海高等研究院 | A kind of preparation method and applications of high performance carbon base carbon dioxide sorbing material |
CN108529588A (en) * | 2018-03-06 | 2018-09-14 | 河南工程学院 | The preparation method of ordered mesoporous carbon |
CN109748279A (en) * | 2019-02-21 | 2019-05-14 | 南京大学 | One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application |
Also Published As
Publication number | Publication date |
---|---|
CN104310396B (en) | 2016-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | Progress and current challenges for CO2 capture materials from ambient air | |
Nguyen et al. | A novel removal of CO2 using nitrogen doped biochar beads as a green adsorbent | |
He et al. | Structure design of a hyperbranched polyamine adsorbent for CO 2 adsorption | |
CN109201007B (en) | Carbon dioxide adsorbent and preparation method and application thereof | |
CN101816924A (en) | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof | |
D'Alessandro et al. | Toward carbon dioxide capture using nanoporous materials | |
CN105233802B (en) | One kind doping arginic copper base metal organic framework materials of L and preparation method thereof | |
CN103203159B (en) | Method for separating nitrous oxide and carbon dioxide by using zeolite-like molecular sieve skeleton material | |
CN106563418A (en) | Preparation of nitrogen-enriched organic porous material, and organic porous material and application thereof | |
CN104310396B (en) | A kind of efficient adsorption CO 2the preparation method of gac | |
CN102389686A (en) | Separating method for CO2-containing mixed gas | |
CN104226260A (en) | Preparation and modification methods of metal-organic frame material Bi-BTC for adsorbing CO2 | |
CN107442084A (en) | A kind of poly-dopamine pitch base composite porous carbon adsorbing material of Preferential adsorption ethane and preparation method and application | |
CN103933939A (en) | Metal-organic framework MOF material with high methane adsorption and storage density | |
CN113368825A (en) | Fluorine cluster-based metal organic framework MFOFs material with high stability and application thereof | |
CN105597705B (en) | One kind has excellent CO2Absorption and the ultramicropore covalent triazine framework material and preparation method of separating property | |
CN113842885A (en) | Metal anchoring organic amine CO2Adsorbent, preparation and application thereof | |
Janetaisong et al. | Pelletization of iron oxide based sorbents for hydrogen sulfide removal | |
KR101394462B1 (en) | Hydrzine and Hydrazine Derivatives for Capturing and Releasing of Carbon Dioxide | |
CN111821812B (en) | CO (carbon monoxide)2Absorbent and synthesis and application thereof | |
KR101305454B1 (en) | Carbon adsorbent codoped nitrogen, oxygen, fluorine for carbon dioxide adsorption and manufacturing method thereof | |
CN114849652A (en) | Activated carbon-encapsulated imidazole metal organic framework composite material with high gas separation selectivity and preparation method thereof | |
CN101298037A (en) | Adsorbing agent for removing trace amount of nitric oxide in carbon dioxide and preparation | |
CN103120931A (en) | Cage type carbon dioxide adsorption material as well as preparation method and application thereof | |
CN106986958A (en) | A kind of preparation method of the polyaminoacid ionic liquid of absorbing acid gases |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |