CN108499532A - A kind of preparation method of the nitrogen-dopped activated carbon of the discarded shell of hydrogen peroxide pre-oxidation - Google Patents
A kind of preparation method of the nitrogen-dopped activated carbon of the discarded shell of hydrogen peroxide pre-oxidation Download PDFInfo
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- CN108499532A CN108499532A CN201810162710.2A CN201810162710A CN108499532A CN 108499532 A CN108499532 A CN 108499532A CN 201810162710 A CN201810162710 A CN 201810162710A CN 108499532 A CN108499532 A CN 108499532A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
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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
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- 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
Abstract
The invention discloses the preparation methods that a kind of hydrogen peroxide pre-oxidizes the nitrogen-dopped activated carbon for discarding shell, and steps are as follows：Hydro-thermal after pretreated discarded shell and distilled water are mixed, obtains the presoma of charcoal, it is mixed with hydrogen peroxide, urea, alkaline metal oxalate successively, obtains activating preceding suspension；By dry, grinding, roasting, washing, drying and other steps, the nitrogen-dopped activated carbon adsorbent is made successively in suspension.The present invention is cheap and easy to get with raw material, preparation condition is mild and obtained adsorbent is at room temperature to CO2Adsorbance it is high, circular regeneration absorption property is good, CO2/N2The advantages that selective absorption is preferable.The specific surface area of prepared nitrogen-dopped activated carbon reaches as high as 1563.42m2/ g, at normal temperatures and pressures to CO2Adsorbance up to 3.94mmol/g, and its adsorbance still maintains stable after circulation absorption 25 times, is the 96% of initial adsorption amount；At normal temperatures and pressures to CO2/N2Adsorptive selectivity up to 64.03.
Description
Technical field
The present invention relates to CO2Capture, especially a kind of CO absorption at room temperature2Discarded shell matrix activated carbon adsorbent
Preparation method.
Background technology
It is the maximum CO in the whole world with the thermal power plant that combustion of fossil fuel generates electricity2Emission source accounts for about CO2Total release
35%.After fuel combustion, precombustion and burning in three kinds of carbon catching methods, CO is captured from the flue gas after burning2It is most
Simple method.Flue gas (200 DEG C of T ＜) after burning is mainly CO2And N2Mixture, but because of CO2Dividing relatively low leads to it
Separating difficulty is very big, in some sense, it has also become restricts the important scientific problems of 21 century world's energy-saving and emission-reduction pattern.Cause
This, to low temperature CO2It adsorbed, recycled with highly important practical significance.
Currently, trapping low temperature CO2Main method have solvent absorption, porous solid absorption method and membrane separation process etc..Its
Middle solvent absorption has strong corrosive, absorbent regeneration energy consumption big equipment and is easily aoxidized degradable；Membrane separation process, which exists, to be divided
From the problems such as less efficient, of high cost, its application is limited.In contrast, the operation of solid absorption method is relatively easy, to equipment
Corrosivity is small, is the CO of a great promotion prospect2Trap recovery technology.Report that more low temperature adsorbent includes zeolite, divides
Sub- sieve, activated carbon, metal organic framework compound etc..
CN102092711A discloses a kind of method that Chinese medicine slag prepares activated carbon, Chinese medicine slag is cleaned in advance, in 100-
It is dried at 120 DEG C, is ground into powder, be soaked in Chinese medicine slag powder in the phosphoric acid that mass concentration is 40% by a certain percentage, used
Ultrasonic wave impregnates 25min, and the Chinese medicine slag powder impregnated is placed in micro-wave oven and is heated, and after stopping heating, 1h is boiled in a covered pot over a slow fire in stove, is taken
It is 6.5-7.0 to be washed to pH with 80-90 DEG C of distilled water or deionized water after going out, and drying obtains activated carbon.Though this method
It is so simple for process, but raw material is not easy to obtain, and activated carbon hole made from phosphoric acid activation method is uneven, specific surface area is smaller, absorption
Effect is poor.CN102211767A discloses a kind of shinyleaf yellowhorn fruit shell granular active carbon and preparation method thereof, by shinyleaf yellowhorn fruit shell powder
It is dry after broken, sieving pretreatment, then crush, acidleach, drying, activation, rinsing, drying, be sieved to obtain finished activated charcoal.This method work
Skill is simple, and salvage value is high, but shiny-leaved yellowhorn is grown in specific region, is not easy to obtain, and significantly limits the system of activated carbon
It is standby.
Hydro-thermal charring (HTC) refers in the pressure vessel of sealing, using compound as raw material, using water as solvent and reaction
Medium, in the process for synthesizing rich carbon product from pressure and 150~375 DEG C.Compared with traditional thermochemical study method, HTC temperature
Spend low, raw material is not limited by moisture, and energy consumption is few, CO2Burst size is few, has become a kind of efficient biomass pretreatment hand
Section and biomass full constituent method for transformation；And hydro-thermal charcoal oxygen-containing functional group is abundant, surface chemical property is adjustable, calorific value is high, in gold
Belong to the fields such as ionic adsorption, the preparation of porous carbon material, solid acid catalyst and clean energy resource and has made some progress (Wu Yan
Handsome, Li Wei, Wu Qiong wait the preparation of hydro-thermal charcoals, property and application [J] chemical progress, 2015,28 (1):121-130.).It is common
Activator such as KOH, the H prepared for activated carbon3PO4、ZnCl2Deng having the shortcomings that corrosivity is strong, pollution is big, of high cost.But with
A variety of oxalates (Li2C2O4、Na2C2O4、K2C2O4Deng) it is that activator is prepared for room temperature CO absorption2Activated carbon research but
It is rarely reported.CN106517181A discloses a kind of efficient absorption CO2Biomass-based activated carbon preparation method, by discarded life
It is uniformly mixed with potassium oxalate after the pretreatment of substance shell, and in N2Static roasting under atmosphere, washed, dry obtained activated carbon.This
Patent further uses H on this basis2O2Etc. preprocessing means, regulate and control the surface chemical property of abandoned biomass, enhance its suction
Attached effect.Guo et al. (Guo L, Yang J, Hu G, et al.Role of Hydrogen Peroxide Preoxidizing
on CO2Adsorption of Nitrogen-Doped Carbons Produced from Coconut Shell[J].Acs
Sustainable Chemistry＆Engineering, 2016,4 (5)) use H2O2Pretreatment, ammonia catalysis and KOH activation
The method of cocoanut shell is prepared with efficient CO2The acticarbon of absorption property, but its catalyst and activator use pair
Equipment requirement is high, unfriendly to environment.Based on this, it is activator using discarded shell as carbon source, alkaline metal oxalate, passes through H2O2
Etc. preprocessing means prepare with CO absorption at room temperature2Nitrogen-dopped activated carbon just have stronger competitiveness.
To sum up, research and development preparation method simplicity, mild condition, raw material be cheap, nontoxic and circulation absorption room temperature of good performance
Lower CO absorption2Discarded shell matrix activated carbon material have important scientific value and good application prospect.
Invention content
The technical problem to be solved by the present invention is to：There is provided that a kind of preparation condition is relatively mild, raw material is cheap and nontoxic
The preparation method of discarded shell matrix activated carbon adsorbent, prepared adsorbent is at room temperature to main greenhouse gas CO2Have
Higher adsorbance and the circular regeneration absorption property stablized.
The present invention solves its technical problem and uses technical solution below：
First, shell will be discarded through clean, drying, broken, screening to 20-100 purposes and distilled water mixes and is incorporated in room temperature
Under be stirred well to uniformly, obtain suspension；After suspension hydro-thermal, hydrothermal product is obtained；Secondly, after hydrothermal product is cooled down
Through distilling water washing, 110 DEG C of dry 12h, the presoma of charcoal is obtained, the H for being 10% by the presoma of charcoal and mass fraction2O2It is molten
Liquid mixes, and obtains pre-oxidation suspension；Later, mixing will be mixed with urea, distilled water after pre-oxidation suspension vacuum drying, obtained
To N doping mixture；It is mixed and is activated with alkaline metal oxalate, distilled water after N doping mixture is dried in vacuo
Preceding suspension；Finally, above-mentioned suspension is passed through to the dry 12h at 110 DEG C successively, grinding, roasting, washing, is done at 80 DEG C
The nitrogen-dopped activated carbon is made in dry 12h.Gained acticarbon CO absorption2Afterwards, then at different temperature desorption follows
Ring regenerates.
It is characterized in that in step (1), the discarded shell is peanut shell, walnut shell or green shell, quality with
The volume ratio of distilled water is 1g:15ml；1~3h of mixing time, speed of agitator 600r/min.
It is characterized in that in step (1), the hydrothermal condition is：180~240 DEG C of hydrothermal temperature, the hydro-thermal time 10~
14h。
It is characterized in that in step (2), the presoma of the charcoal and 10% H2O2The mixed proportion of solution is 1g:10ml.
It is characterized in that in step (3), the vacuum drying process conditions of the pre-oxidation suspension are：It is dry at 60 DEG C
12h；Pre-oxidize dried object：Urea=1g：0.15~0.5g, 60~100ml of distilled water.
It is characterized in that in step (4), the alkaline metal oxalate is Li2C2O4、Na2C2O4、K2C2O4In one kind；Institute
Each material quality ratio of solution is N doping dried object before stating activation：Alkaline metal oxalate：Distilled water=1g：1~5g：10ml is stirred
Mix the time for 24 hours, rotating speed 600r/min；The vacuum drying process conditions are：It is dried for 24 hours at 60 DEG C.
It is characterized in that in step (5), the process conditions of the roasting are：N2Static roasting, calcination temperature 500 under atmosphere
~700 DEG C, 1~2h of roasting time.
It is characterized in that the specific surface area of prepared nitrogen-dopped activated carbon reaches as high as 1563.42m2/g。
It is characterized in that prepared nitrogen-dopped activated carbon is at normal temperatures and pressures to CO2Adsorbance up to 3.94mmol/g,
And after circulation absorption 25 times its adsorbance also without there is apparent downward trend, still 96% for initial adsorption amount；To CO2/N2
Adsorptive selectivity up to 64.03.
Compared with prior art, the present invention has following major advantage：
(1) preparation condition is mild, including selects discarded shell cheap and easy to get and nontoxic as carbon source；Select temperature
With and alkaline metal oxalate of good performance as activator；
(2) predecessor of charcoal is made using mild hydro-thermal reaction；By preprocessing means such as hydrogen peroxide, then fired
To acticarbon, the absorption property of activated carbon is greatly improved on the basis of reducing energy consumption；
(3) the biomass-based activated carbon prepared by can be regenerated at a lower temperature (by CO absorption2Sample afterwards is in the U.S.
Micro meritics instrument companies production II 3020 type Sorption Analyzer degassers of first generation TriStar in 200 DEG C,
Deaerate 4h under vacuum condition, you can completes regeneration tests), and there is excellent circular regeneration absorption property.
Description of the drawings
Fig. 1 is that N doping prepared by Examples 1 to 8 discards shell matrix activated carbon at normal temperatures and pressures to CO2Absorption it is bent
Line.
Fig. 2 is the scanning electron microscopic picture that N doping discards shell matrix activated carbon prepared by embodiment 1.
Fig. 3 is the X-ray diffractogram that N doping discards shell matrix activated carbon prepared by embodiment 1.
Fig. 4 is the discarded shell matrix activated carbon of N doping prepared by embodiment 1 at normal temperatures and pressures to CO2Circulation absorption
Block diagram.
In Fig. 5, figure a, b are respectively Examples 1 to 4, N doping prepared by 5~8 discards the N of shell matrix activated carbon2Absorption-
Desorption curve.
In Fig. 6, figure a, b are respectively Examples 1 to 4, N doping prepared by 5~8 discards the pore size distribution of shell matrix activated carbon
Curve.
In Fig. 7, figure a, b are respectively biomass-based activated carbon prepared by embodiment 6 at normal temperatures and pressures to CO2And N2's
Adsorption curve, at normal temperatures and pressures to CO2/N2The initial slope measurement chart of adsorption curve.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is further illustrated, these embodiments be only to the present invention compared with
The description of good embodiment, but it is not limited to the following content.
Embodiment 1：
First, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distilled water
Stirring 2h obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal at 240 DEG C
12h obtains hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g:10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.25g, distilled water 40ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
K2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 700 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 3.94mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 15.05.
Embodiment 2：
First, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distilled water
Stirring 2h obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal at 240 DEG C
12h obtains hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g:10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.25g, distilled water 75ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
K2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 700 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 2h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 2.71mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 16.69.
Embodiment 3：
First, it will clean, the walnut shell after drying is at powder to 20-100 mesh；Take 4g walnut shell powders, 60ml distilled water in room
The lower stirring 3h of temperature obtains suspension；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal 12h at 240 DEG C,
Obtain hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g:10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.25g, distilled water 75ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
K2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:5g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 700 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 2h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 2.87mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 16.70.
Embodiment 4：
First, it will clean, the peanut shell after drying is at powder to 20-100 mesh；Take 4g peanut shell powders, 60ml distilled water in room
The lower stirring 1h of temperature obtains suspension；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal 12h at 240 DEG C,
Obtain hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g：10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.25g, distilled water 75ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
K2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 700 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 2h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 2.75mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 13.68.
Embodiment 5：
First, it will clean, the walnut shell after drying is at powder to 20-100 mesh；Take 4g walnut shell powders, 60ml distilled water in room
The lower stirring 2h of temperature obtains suspension；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal 10h at 210 DEG C,
Obtain hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g：10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.50g, distilled water 80ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
Na2C2O4, distilled water mix (dried object：Na2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 500 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 1.17mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 63.65.
Embodiment 6：
First, it will clean, the peanut shell after drying is at powder to 20-100 mesh；Take 4g peanut shell powders, 60ml distilled water in room
The lower stirring 1h of temperature obtains suspension；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal 10h at 210 DEG C,
Obtain hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g:10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.50g, distilled water 80ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
Na2C2O4, distilled water mix (dried object：Na2C2O4：Distilled water=1g:1g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 500 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 1.13mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Adsorptive selectivity be 64.03.
Embodiment 7：
First, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distilled water
Stirring 2h obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal at 180 DEG C
14h obtains hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g：10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.15g, distilled water 100ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
K2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 600 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 2.99mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Selectivity be 23.86.
Embodiment 8：
First, it will clean, the peanut shell after drying is at powder to 20-100 mesh；Take 4g peanut shell powders, 60ml distilled water in room
The lower stirring 1h of temperature obtains suspension；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the hydro-thermal 14h at 180 DEG C,
Obtain hydrothermal product；
Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h, obtains the forerunner of charcoal
Body；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2Solution=1g：10ml),
Obtain mixed liquor；
Later, mixed liquor is dried in vacuo after 12h at 60 DEG C and mixes (dried object with urea, distilled water：Urea=1g：
0.15g, distilled water 80ml), obtain the mixture of N doping；N doping mixture be dried in vacuo at 60 DEG C for 24 hours after with
Li2C2O4, distilled water mix (dried object：Li2C2O4：Distilled water=1g:3g:10ml), stirring obtains activating preceding solution for 24 hours afterwards；
Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2In 600 DEG C of charings under (50ml/min) atmosphere
(heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water wash repeatedly to it is neutral,
Biomass-based activated carbon is obtained after dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be 1.42mmol/g (see Fig. 1
Curve), at normal temperatures and pressures to CO2/N2Selectivity be 26.66.
In order to probe into H2O2It is right at room temperature whether pre-oxidation and N doping processing method can effectively improve absorbent charcoal material
CO2Adsorption capacity, following three groups of control experiments are designed under preferable experiment condition (embodiment 1)：
(1) first, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distillations
Water stirs 2h and obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the water at 240 DEG C
Hot 12h, obtains hydrothermal product；Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h,
Obtain the presoma of charcoal；The H for being 10% by carbon precursor and mass fraction2O22h (carbon precursors are mixed in solution:H2O2It is molten
Liquid=1g:10ml)；Later, mixed liquor is dried in vacuo at 60 DEG C after 12h and K2C2O4, distilled water mix (dried object：
K2C2O4：Distilled water=1g:3g:10ml) stirring for 24 hours, obtains activating preceding solution；Finally, by solution before activation through drying (110
DEG C), grind, be placed in N2The lower 700 DEG C of charings of (50ml/min) atmosphere (heating rate is 5 DEG C/min) 1h, obtains carbide；By charcoal
Compound obtains biomass-based activated carbon after 1mol/L hydrochloric acid and distilled water are washed repeatedly to neutral, dry (80 DEG C), normal
To CO under normal temperature and pressure2Adsorbance be 2.78mmol/g.
(2) first, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distillations
Water stirs 2h and obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the water at 240 DEG C
Hot 12h, obtains hydrothermal product；Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h,
Obtain the presoma of charcoal；The presoma of charcoal is mixed into (dried object with urea, distilled water：Urea=1g：0.25g, distilled water
40ml) obtain N doping mixture；N doping mixture is dried in vacuo to rear and K for 24 hours at 60 DEG C2C2O4, distilled water mixing it is (dry
Dry object：K2C2O4：Distilled water=1g:3g:Solution before 10ml) stirring must activate for 24 hours；Finally, by solution before activation through drying (110
DEG C), grind, be placed in N2The lower 700 DEG C of charings of (50ml/min) atmosphere (heating rate is 5 DEG C/min) 1h, obtains carbide；By charcoal
Compound obtains biomass-based activated carbon after 1mol/L hydrochloric acid and distilled water are washed repeatedly to neutral, dry (80 DEG C), normal
To CO under normal temperature and pressure2Adsorbance be 2.88mmol/g.
(3) first, it will clean, green shell after drying is at powder to 20-100 mesh；Take green shell powder of 4g, 60ml distillations
Water stirs 2h and obtains suspension at room temperature；Suspension is transferred to in the reaction kettle of inner liner polytetrafluoroethylene the water at 240 DEG C
Hot 12h, obtains hydrothermal product；Secondly, hydrothermal product is placed in after cooling down at room temperature through distilling water washing, 110 DEG C of dry 12h,
Obtain the presoma of charcoal；By the presoma and K of charcoal2C2O4, distilled water mix (dried object：K2C2O4：Distilled water=1g:3g:
Solution before 10ml) stirring must activate for 24 hours；Finally, by solution before activation through drying (110 DEG C), grind, be placed in N2(50ml/min)
The lower 700 DEG C of charings of atmosphere (heating rate is 5 DEG C/min) 1h, obtains carbide；By carbide through 1mol/L hydrochloric acid and distilled water
Biomass-based activated carbon is obtained after being washed repeatedly to neutral, dry (80 DEG C), at normal temperatures and pressures to CO2Adsorbance be
2.87mmol/g。
II 3020 types of the TriStar absorption point produced using Micro meritics instrument companies of the U.S. in above-described embodiment
Analyzer analyzes the specific surface area and hole of sample, and total specific surface area is measured using BET method, and total pore volume is in relative pressure
(P/P0) be calculated by the adsorbance of liquid nitrogen for 0~0.995；Sample is at normal temperatures and pressures to CO2And N2Adsorbance using beautiful
II 3020 type Sorption Analyzers of the TriStar test of Micromeritics instrument companies of state production, CO2/N2Selectivity pass through
CO2And N2The initial slope of adsorption curve is calculated with Henry's law；The microstructure of sample surfaces is to use Japan Electronics strain
The JSM-IT300 type scanning electron microscope tests of formula commercial firm production；The phase structure of sample uses Brooker AXS companies of Germany
D8Advance type X-ray diffractometers detection.
The scanning electron microscope diagram piece (Fig. 2) of discarded shell matrix activated carbon prepared by according to embodiments of the present invention 1 can
Know, which is the multi-pore channel amorphous carbon with layer structure.
Its wide-angle known to the X-ray diffractogram (Fig. 3) of discarded shell matrix activated carbon prepared by according to embodiments of the present invention 1
XRD is to have wider (002) and (100) crystallographic plane diffraction peak at 23 ° and 43 ° in 2 θ, shows that the product is mostly to have random layer knot
The amorphous carbon of structure.
The analyses such as the specific surface area of sample and pore structure the results are shown in Table 1 in Examples 1 to 8.As can be seen from Table 1, root
There is higher total specific surface area and total hole volume, highest according to the discarded shell matrix activated carbon prepared by the embodiment of the present invention 1~8
Respectively up to 1563.42m2/g、0.67cm3/ g, and CO2A diameter of 0.33nm of molecule, therefore activated carbon pair prepared by the present invention
CO2There is preferable adsorption effect.
By the sample of embodiment 1 through CO absorption2Afterwards in the TriStar II of Micro meritics instrument companies of U.S. production
Deaerate on 3020 type Sorption Analyzer degassers under 200 DEG C, vacuum condition 4h.Then the sample after degassing is recycled
Adsorption experiment recycles 25 times, to room temperature CO2Adsorbance is still up to 3.78mmol/g, is initial adsorption amount (3.94mmol/g)
96%, show excellent circular regeneration use ability (see Fig. 4).
The N of discarded shell matrix activated carbon prepared by according to embodiments of the present invention 1~82Adsorption-desorption curve (Fig. 5) and
Pore distribution curve (Fig. 6) is it is found that sample shows typical meso-hole structure, microcellular structure and micro- meso-hole structure.In conjunction with main in table 1
Want texture nature parameters and CO2The variation tendency of adsorbance can speculate the physical factors pair such as specific surface area and the pore structure of sample
Its absorption property may play a decisive role.
The CO of discarded shell matrix activated carbon at normal temperatures and pressures prepared by according to embodiments of the present invention 62And N2Adsorption curve
See Fig. 7, low-down N is shown at 25 DEG C, under the conditions of 1bar2Adsorbance, only 0.10mmol/g, this shows that the sample can
For being selectively adsorbing and separating CO2And N2CO in mixed gas2。CO2/N2Selectivity be to pass through CO2And N2Adsorption curve
Initial slope be calculated with Henry's law, specific method is shown in Fig. 7, and the selectivity that is thus calculated is 64.03.According to
Biomass-based activated carbon prepared by the embodiment of the present invention 1~8 is at normal temperatures and pressures to CO2/N2Adsorptive selectivity design parameter
It is shown in Table 1.
In above-described embodiment, former occupation may be usedMultifunctional crusher crushes sample, and the product after crushing is
20-100 mesh.
Main Texture nature parameters of discarded active fruit shell carbon prepared by 1 Examples 1 to 8 of table and its at normal temperatures and pressures
Absorption result
Claims (9)
1. the preparation method of the nitrogen-dopped activated carbon of shell is discarded in a kind of hydrogen peroxide pre-oxidation, it is characterized in that including the following steps：
(1) will through cleaning, drying, broken, screening to 20-100 purposes discard shell and be mixed with distilled water and abundant at room temperature
It is stirred until homogeneous, obtains suspension；After suspension hydro-thermal, hydrothermal product is obtained；
(2) through distilling water washing, 110 DEG C of dry 12h after cooling down hydrothermal product, the presoma of charcoal is obtained, by the presoma of charcoal
The H for being 10% with mass fraction2O2Solution mixes, and obtains pre-oxidation suspension；
(3) it will be mixed with urea, distilled water after pre-oxidation suspension vacuum drying, and obtain N doping mixture；
(4) it is mixed, is lived with certain proportion with alkaline metal oxalate, distilled water after being dried in vacuo N doping mixture
Suspension before changing；
(5) by above-mentioned suspension successively by dry 12h, grinding, roasting, washing, the dry 12h at 80 DEG C, system at 110 DEG C
Obtain the nitrogen-dopped activated carbon.
2. preparation method according to claim 1, it is characterised in that in step (1), the discarded shell be peanut shell,
The volume ratio of walnut shell or green shell, quality and distilled water is 1g:15ml；1~3h of mixing time, speed of agitator 600r/
min。
3. preparation method according to claim 1, it is characterised in that in step (1), the hydrothermal condition is：Hydro-thermal temperature
180~240 DEG C of degree, 10~14h of hydro-thermal time.
4. preparation method according to claim 1, it is characterised in that in step (2), the presoma of the charcoal and 10%
H2O2The mixed proportion of solution is 1g:10ml.
5. preparation method according to claim 1, it is characterised in that in step (3), the pre-oxidation suspension vacuum is dry
Dry process conditions are：The dry 12h at 60 DEG C；Pre-oxidize dried object：Urea=1g：0.15~0.5g, distilled water 60~
100ml。
6. preparation method according to claim 1, it is characterised in that in step (4), the alkaline metal oxalate is
Li2C2O4、Na2C2O4、K2C2O4In one kind；
Each material quality ratio of solution is N doping dried object before the activation：Alkaline metal oxalate：Distilled water=1g：1~5g：
10ml, mixing time for 24 hours, rotating speed 600r/min；The vacuum drying process conditions are：It is dried for 24 hours at 60 DEG C.
7. preparation method according to claim 1, it is characterised in that in step (5), the process conditions of the roasting are：N2
Static roasting, 500~700 DEG C of calcination temperature, 1~2h of roasting time under atmosphere.
8. nitrogen-dopped activated carbon prepared by the method according to claim 1-7, it is characterised in that the nitrogen-dopped activated carbon
Specific surface area reaches as high as：1563.42m2/g。
9. nitrogen-dopped activated carbon prepared by the method according to claim 1-7, it is characterized in that at normal temperatures and pressures to CO2's
Adsorbance is up to 3.94mmol/g, and its adsorbance is still first also without there is apparent downward trend after circulation absorption 25 times
The 96% of beginning adsorbance；To CO2/N2Adsorptive selectivity up to 64.03.
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| CN111346663A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Amino resin modified nitrogen-doped activated carbon catalyst and preparation method and application thereof |
| CN113149006A (en) * | 2021-05-12 | 2021-07-23 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
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| CN113149006A (en) * | 2021-05-12 | 2021-07-23 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
| CN113149006B (en) * | 2021-05-12 | 2021-11-02 | 广西科学院 | Method for preparing capacitance carbon by using biomass rich in lignin as raw material |
| CN114700036A (en) * | 2022-03-25 | 2022-07-05 | 华南理工大学 | Modified tobacco stem-based biomass hierarchical pore carbon and preparation method and application thereof |
| CN114700036B (en) * | 2022-03-25 | 2023-09-29 | 华南理工大学 | Modified tobacco stem-based biomass hierarchical porous carbon and preparation method and application thereof |
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Application publication date: 20180907 |