CN103949216A - Preparation method of carbon material for adsorbing hydrophilic ionic liquid - Google Patents
Preparation method of carbon material for adsorbing hydrophilic ionic liquid Download PDFInfo
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- CN103949216A CN103949216A CN201410199790.0A CN201410199790A CN103949216A CN 103949216 A CN103949216 A CN 103949216A CN 201410199790 A CN201410199790 A CN 201410199790A CN 103949216 A CN103949216 A CN 103949216A
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Abstract
The invention provides a preparation method of a carbon material for adsorbing hydrophilic ionic liquid. The method comprises the following steps: performing hydrothermal reaction on cellulose which serves as a raw material in a high-pressure hydrothermal reaction kettle to obtain carbon microspheres rich in oxygen-containing groups such as hydroxyl and carboxyl; and activating the carbon microspheres in a muffle furnace by using KOH under the protection of nitrogen atmosphere to obtain a spongy carbon material with the large specific surface area and the surface rich in the oxygen-containing groups. The carbon microspheres with the surface rich in the oxygen-containing groups can be obtained by incomplete hydrothermal carbonization of the cellulose, the specific surface area of the carbon material can be greatly improved by KOH activation under the condition of retaining oxygen-containing chemical groups on the surface, a pore channel structure is improved, a carbon material adsorbent with unique hydrophilic ionic liquid adsorption performance is finally obtained, and the adsorption efficiency and the adsorption capacity are greatly improved. The needed raw materials are common and easily available, the preparation method is simple, and the obtained carbon material adsorbent has good effects on adsorption and recycling of the hydrophilic ionic liquid in wastewater.
Description
Technical field
The invention belongs to preparation and environment and the Application in Chemical Engineering field of living beings class adsorbent, specifically, the incomplete hydrothermal carbonization and the KOH thereof that relate to by cellulose biomass activate, thereby obtain high-specific surface area and pore volume while rich surface containing the method for the material with carbon element adsorbent containing oxygen functional group.
Background technology
When referring at normal temperature or approach normal temperature, ionic liquid in liquid salt, conventionally by organic cation and inorganic anion, formed.Because ionic liquid has good heat endurance and the vapour pressure that can't detect, thereby be considered to a kind of green solvent all the time and be widely used in the fields such as material preparation, energy storage, living beings utilization, chemical industry, catalysis and environmental analysis.But nearest result of study shows that ionic liquid exists certain toxicity to biologies such as flea, algae, zebra fish, earthworms, thereby environment and the ecosystem are existed to certain potential risk.Due to the stability of ionic liquid, be difficult to decompose by chemical method, be also difficult to be degraded by microorganisms, therefore absorption is to a kind of effective ways of ionic liquid being separated from waste water before environment at ionic liquid discharge of wastewater.
Active carbon is the conventional adsorbent of adion liquid at present, although but traditional method for preparation of active carbon makes it have huge specific area, but the oxy radical on surface seldom, its surface is hydrophobic, thereby traditional active carbon only has good adsorption effect to hydrophobic ionic liquid, and not good to hydrophilic ionic liquid adsorption effect.Therefore, for using the processing of hydrophilic ionic-liquid more widely, need to develop the preparation method of new adsorbent, prepared adsorbent is except having huge specific area and pore volume, and abundant polar group also should be contained in its surface.
In the present invention, we utilize cellulosic incomplete hydrothermal carbonization, obtain being rich in the carbosphere of the function group such as hydroxyl and carboxyl.The oxygen content of this carbosphere is very high, but due to the very low (220-280 of carburizing temperature
oc), thus specific area very little.This carbosphere is further activated with KOH under nitrogen atmosphere, obtained having the material with carbon element adsorbent of large specific area and oxy radical simultaneously.Compare with traditional active carbon, this adsorbent improves greatly to the adsorption capacity of hydrophilic ionic-liquid.
Successively utilize the method preparation of this cellulosic hydrothermal carbonization and KOH activation to there is the method for the carbon adsorbent of larger specific area and high polarity oxy radical simultaneously, and the absorption for polar by it, there is not yet before this report.
Summary of the invention
The present invention is directed to the problem that traditional active carbon is little to hydrophilic ionic-liquid adsorption capacity, adsorption efficiency is low, a kind of method of preparing novel cellulose base material with carbon element adsorbent is provided, this adsorbent is high to hydrophilic ionic-liquid adsorption efficiency, adsorption capacity is large, and can recycle.
The preparation method of the material with carbon element of the absorption hydrophilic ionic-liquid that the present invention proposes, is to take fiber rope as raw material, utilizes successively cellulosic incomplete hydrothermal carbonization and KOH activation to obtain the spongy material with carbon element adsorbent of black.This material specific area is 900 ~ 1500 m
2/ g, pore volume is at 0.4 ~ 0.9 cm
3/ g, carbon content is 55 ~ 75%, and oxygen content is 20 ~ 40%, the functional groups such as rich surface hydroxyl, carboxyl.Specifically comprise the following steps:
(1) under magnetic agitation, successively add the microcrystalline cellulose of 1 ~ 4 mass parts and the distilled water of 10 mass parts, continue to stir 30min;
(2) mixed liquor of step (1) preparation is proceeded in the stainless steel autoclave of inner liner polytetrafluoroethylene to heated sealed to 220 ~ 280
oc constant temperature 6 ~ 12h, 1000 revs/min of rotating speeds stir;
(3) reaction is cooled to room temperature after finishing, and distilled water and alternately washing of ethanol for the black powder of generation, remove whole moisture in 80 ℃ of freeze-day with constant temperature 12h, obtains particle diameter at the carbosphere of 3 ~ 5 microns;
(4) after the carbosphere material obtaining in step (3) and KOH powder are mixed with the mass ratio of 1:1 to 1:4, put into Muffle furnace, pass into nitrogen, under nitrogen atmosphere 600
ounder C, heat treatment is 1 ~ 6 hour;
(5) solid obtaining in step (4) alternately cleans to pH and is neutral with the HCl solution of 0.1 ~ 1 mol/L and distilled water, in 80 ℃ of freeze-day with constant temperature 12h, obtains being the material with carbon element of the absorption hydrophilic ionic-liquid of black;
(6) this material with carbon element proves that after SEM, FT-IR and elementary analysis it is the spongy carbon material that contain-OH of rich surface ,-COOH, C=O etc. contain oxygen functional group.
[advantage of the present invention and good effect]:
The present invention has following advantages: the one, and the raw material sources of absorbent preparation are the biomass celluloses that nature extensively exists, they are reproducible, wide material sources; The 2nd, the hydrothermal carbonization adopting in absorbent preparation process and follow-up activation temperature are relatively low; Easy operating and the saving energy; The 3rd, the adsorbent preparing not only has huge specific area and pore volume, and rich surface contains oxygen functional group containing polarity, it has better absorption property to hydrophilic ionic-liquid, adsorbance to typicalness hydrophilic ionic-liquid 1-butyl-3-methylimidazole bromine salt reaches 102.9 mg/g, is 4 times of common active carbon.In addition, adsorption and enrichment is easy to reclaim by pickling desorption to the ionic liquid on adsorbent, and sorbent circulation is used.
[accompanying drawing explanation]:
Fig. 1 is ESEM (SEM) figure of the carbosphere that obtains of cellulosic incomplete hydrothermal carbonization, and Fig. 2 is that hydro-thermal carbosphere is further with ESEM (SEM) figure of the spongy material with carbon element adsorbent obtaining after KOH activation.
[specific embodiment]:
embodiment 1:
(1) under magnetic agitation, successively add the microcrystalline cellulose of 20 g and the distilled water of 60 mL, continue to stir 30min;
(2) mixed liquor of step (1) preparation is proceeded in the stainless steel autoclave of inner liner polytetrafluoroethylene to heated sealed to 250
oc constant temperature 10 h, 1000 revs/min of rotating speeds stir;
(3) reaction is cooled to room temperature after finishing, and distilled water and alternately washing of ethanol for the black powder of generation, remove whole moisture in 80 ℃ of freeze-day with constant temperature 12h, obtains particle diameter at the carbosphere of 3 ~ 5 microns;
(4) after the carbosphere material obtaining in step (3) and KOH powder are mixed with the mass ratio of 1:4, put into Muffle furnace, pass into nitrogen, under nitrogen atmosphere 600
ounder C, heat treatment is 2 hours;
(5) solid obtaining in step (4) alternately cleans to pH and is neutral with the HCl solution of 1 mol/L and distilled water, in 80 ℃ of freeze-day with constant temperature 12h, obtains being the material with carbon element of the absorption hydrophilic ionic-liquid of black;
(6) this material with carbon element proves that after SEM, FT-IR and elementary analysis it is the spongy carbon material that contain-OH of rich surface ,-COOH, C=O etc. contain oxygen functional group.This material specific area is 1240 m
2/ g, pore volume is at 0.655 cm3/g, carbon content 61%, oxygen content is 36%.
(7) test shows, this material with carbon element adsorbent prepared by the present embodiment, 25
o1-butyl-3-methylimidazole bromine salt ion the liquid aqueous solution (pH 8.0) that is 50 mg/L to 20 mL concentration under C carries out Static Adsorption, and this adsorbent of 0.05 g reaches 98% at 30 min with the interior clearance to 1-butyl-3-methylimidazole bromine salt ion liquid.Adsorption isotherm result of the test shows that its maximal absorptive capacity reaches 65.7 mg/g.
embodiment 2:
(1) under magnetic agitation, successively add the microcrystalline cellulose of 10 g and the distilled water of 60 mL, continue to stir 30min;
(2) mixed liquor of step (1) preparation is proceeded in the stainless steel autoclave of inner liner polytetrafluoroethylene to heated sealed to 260
oc constant temperature 8 h, 1000 revs/min of rotating speeds stir;
(3) reaction is cooled to room temperature after finishing, and distilled water and alternately washing of ethanol for the black powder of generation, remove whole moisture in 80 ℃ of freeze-day with constant temperature 12h, obtains particle diameter at the carbosphere of 3 ~ 5 microns;
(4) after the carbosphere material obtaining in step (3) and KOH powder are mixed with the mass ratio of 1:2, put into Muffle furnace, pass into nitrogen, under nitrogen atmosphere 600
ounder C, heat treatment is 4 hours;
(5) solid obtaining in step (4) alternately cleans to pH and is neutral with the HCl solution of 1 mol/L and distilled water, in 80 ℃ of freeze-day with constant temperature 12h, obtains being the material with carbon element of the absorption hydrophilic ionic-liquid of black;
(6) this material with carbon element proves that after SEM, FT-IR and elementary analysis it is the spongy carbon material that contain-OH of rich surface ,-COOH, C=O etc. contain oxygen functional group.This material specific area is 1040 m
2/ g, pore volume is at 0.565 cm3/g, carbon content 65%, oxygen content is 30%;
(7) test shows, this material with carbon element adsorbent prepared by the present embodiment, 25
o1-butyl-3-methylimidazole bromine salt ion the liquid aqueous solution (pH 8.0) that is 50 mg/L to 20 mL concentration under C carries out Static Adsorption, and this adsorbent of 0.05 g reaches 96% at 30 min with the interior clearance to 1-butyl-3-methylimidazole bromine salt ion liquid.Adsorption isotherm result of the test shows that its maximal absorptive capacity reaches 61.3 mg/g.
embodiment 3:
(1) under magnetic agitation, successively add the microcrystalline cellulose of 20 g and the distilled water of 50 mL, continue to stir 30min;
(2) mixed liquor of step (1) preparation is proceeded in the stainless steel autoclave of inner liner polytetrafluoroethylene to heated sealed to 250
oc constant temperature 12 h, 1000 revs/min of rotating speeds stir;
(3) reaction is cooled to room temperature after finishing, and distilled water and alternately washing of ethanol for the black powder of generation, remove whole moisture in 80 ℃ of freeze-day with constant temperature 12h, obtains particle diameter at the carbosphere of 3 ~ 5 microns;
(4) after the carbosphere material obtaining in step (3) and KOH powder are mixed with the mass ratio of 1:4, put into Muffle furnace, pass into nitrogen, under nitrogen atmosphere 600
ounder C, heat treatment is 2 hours;
(5) solid obtaining in step (4) alternately cleans to pH and is neutral with the HCl solution of 1 mol/L and distilled water, in 80 ℃ of freeze-day with constant temperature 12h, obtains being the material with carbon element of the absorption hydrophilic ionic-liquid of black;
(6) this material with carbon element proves that after SEM, FT-IR and elementary analysis it is the spongy carbon material that contain-OH of rich surface ,-COOH, C=O etc. contain oxygen functional group.This material specific area is 1360 m
2/ g, pore volume is at 0.712 cm3/g, carbon content 59%, oxygen content is 36%;
(7) test shows, this material with carbon element adsorbent prepared by the present embodiment, 25
o1-butyl-3-methylimidazole bromine salt ion the liquid aqueous solution (pH 11.0) that is 50 mg/L to 20 mL concentration under C carries out Static Adsorption, and this adsorbent of 0.05 g reaches 99.5% at 30 min with the interior clearance to 1-butyl-3-methylimidazole bromine salt ion liquid.Adsorption isotherm result of the test shows that its maximal absorptive capacity reaches 102.9 mg/g.
Claims (2)
1. a preparation method of adsorbing the material with carbon element of hydrophilic ionic-liquid, is characterized in that take that cellulose is as raw material, successively through the KOH under incomplete hydrothermal carbonization and nitrogen protection in autoclave, activates two steps and processes, and obtains specific area at 900 ~ 1500 m
2/ g, pore volume is at 0.4 ~ 0.8 cm
3/ g, carbon content is 55 ~ 75%, and oxygen content is at the spongy material with carbon element of the functional groups such as 20 ~ 40% rich surface hydroxyl, carboxyl, and described specific area adopts BET method to measure.
2. the preparation method of the material with carbon element of absorption hydrophilic ionic-liquid as claimed in claim 1, is characterized in that the method is through following steps:
(1) under magnetic agitation, successively add the microcrystalline cellulose of 1 ~ 4 mass parts and the distilled water of 10 mass parts, continue to stir 30min;
(2) mixed liquor of step (1) preparation is proceeded in the stainless steel autoclave of inner liner polytetrafluoroethylene to heated sealed to 220 ~ 280
oc constant temperature 6 ~ 12h, 1000 revs/min of rotating speeds stir;
(3) reaction is cooled to room temperature after finishing, and distilled water and alternately washing of ethanol for the black powder of generation, remove whole moisture in 80 ℃ of freeze-day with constant temperature 12h, obtains particle diameter at the carbosphere of 3 ~ 5 mm;
(4) after the carbosphere material obtaining in step (3) and KOH powder are mixed with the mass ratio of 1:1 to 1:4, put into Muffle furnace, pass into nitrogen, under nitrogen atmosphere 600
ounder C, heat treatment is 1 ~ 6 hour;
(5) solid obtaining in step (4) alternately cleans to pH and is neutral with the HCl solution of 0.1 ~ 1 mol/L and distilled water, in 80 ℃ of freeze-day with constant temperature 12h, obtains being the material with carbon element of the absorption hydrophilic ionic-liquid of black;
(6) this material with carbon element proves that after SEM, FT-IR and elementary analysis it is the spongy material with carbon element that contain-OH of rich surface ,-COOH, C=O etc. contain oxygen functional group.
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Cited By (12)
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| EP2982649A1 (en) * | 2014-08-08 | 2016-02-10 | AVA-Co2 Schweiz AG | Method for the production of high quality activated carbons and activated carbons produced using the method |
| CN105597706A (en) * | 2015-12-23 | 2016-05-25 | 北京化工大学 | Preparation method for porous polymeric ionic liquid for carbon dioxide adsorption |
| CN105664847A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Method for preparing high-specific surface area porous carbon material based on oil tea seed husk and application thereof |
| CN105883805A (en) * | 2016-04-20 | 2016-08-24 | 南昌航空大学 | Preparation method of camellia seed shell based carbon microspheres with high specific surface area |
| CN106345412A (en) * | 2016-10-20 | 2017-01-25 | 南京大学 | Method for removing 1-butyl-3-methylimidazol ionic liquid pollutants out of water through adsorption method |
| US9914679B2 (en) | 2014-12-12 | 2018-03-13 | Uop Llc | Processes for removing entrained ionic liquid from a hydrocarbon phase |
| CN111011161A (en) * | 2019-12-26 | 2020-04-17 | 郑州大学 | Red mud soil matrix and preparation method thereof |
| CN112645307A (en) * | 2021-01-28 | 2021-04-13 | 太原理工大学 | Method for preparing hydrophilic carbon material |
| CN112973628A (en) * | 2021-02-06 | 2021-06-18 | 重庆文理学院 | Preparation method of activated carbon rich in basic functional groups |
| CN113247985A (en) * | 2021-07-09 | 2021-08-13 | 生态环境部华南环境科学研究所 | TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method |
| CN114749211A (en) * | 2022-05-18 | 2022-07-15 | 农业农村部环境保护科研监测所 | Sulfonic acid group carbon microsphere and preparation method and application thereof |
| CN115318257A (en) * | 2022-05-25 | 2022-11-11 | 贵州大学 | Preparation method of sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2982649A1 (en) * | 2014-08-08 | 2016-02-10 | AVA-Co2 Schweiz AG | Method for the production of high quality activated carbons and activated carbons produced using the method |
| US9914679B2 (en) | 2014-12-12 | 2018-03-13 | Uop Llc | Processes for removing entrained ionic liquid from a hydrocarbon phase |
| CN105597706A (en) * | 2015-12-23 | 2016-05-25 | 北京化工大学 | Preparation method for porous polymeric ionic liquid for carbon dioxide adsorption |
| CN105597706B (en) * | 2015-12-23 | 2017-12-12 | 北京化工大学 | A kind of preparation method of porous polymeric ionic liquid for carbon dioxide adsorption |
| CN105664847B (en) * | 2016-01-13 | 2018-08-17 | 南昌航空大学 | A kind of preparation and application of the porous carbon materials of the high-specific surface area based on tea seed shell base |
| CN105664847A (en) * | 2016-01-13 | 2016-06-15 | 南昌航空大学 | Method for preparing high-specific surface area porous carbon material based on oil tea seed husk and application thereof |
| CN105883805A (en) * | 2016-04-20 | 2016-08-24 | 南昌航空大学 | Preparation method of camellia seed shell based carbon microspheres with high specific surface area |
| CN105883805B (en) * | 2016-04-20 | 2018-01-12 | 南昌航空大学 | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base |
| CN106345412A (en) * | 2016-10-20 | 2017-01-25 | 南京大学 | Method for removing 1-butyl-3-methylimidazol ionic liquid pollutants out of water through adsorption method |
| CN111011161A (en) * | 2019-12-26 | 2020-04-17 | 郑州大学 | Red mud soil matrix and preparation method thereof |
| CN112645307A (en) * | 2021-01-28 | 2021-04-13 | 太原理工大学 | Method for preparing hydrophilic carbon material |
| CN112973628A (en) * | 2021-02-06 | 2021-06-18 | 重庆文理学院 | Preparation method of activated carbon rich in basic functional groups |
| CN113247985A (en) * | 2021-07-09 | 2021-08-13 | 生态环境部华南环境科学研究所 | TBBPA-containing sewage treatment method, porous carbon microsphere material and preparation method |
| CN114749211A (en) * | 2022-05-18 | 2022-07-15 | 农业农村部环境保护科研监测所 | Sulfonic acid group carbon microsphere and preparation method and application thereof |
| CN114749211B (en) * | 2022-05-18 | 2023-11-03 | 农业农村部环境保护科研监测所 | Sulfonic carbon microsphere and preparation method and application thereof |
| CN115318257A (en) * | 2022-05-25 | 2022-11-11 | 贵州大学 | Preparation method of sauce-flavor wine vinasse-based porous carbon composite ionic liquid gas adsorbent |
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Application publication date: 20140730 |