CN105776178B - It is a kind of to utilize nitrogen sulphur codope porous charcoal of organic point of preparation of DCL/Direct coal liquefaction heavy and its preparation method and application - Google Patents
It is a kind of to utilize nitrogen sulphur codope porous charcoal of organic point of preparation of DCL/Direct coal liquefaction heavy and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of method that nitrogen sulphur codope porous charcoal is prepared using coal directly-liquefied residue heavy organics, this method comprises the following steps：(1) by DCL/Direct coal liquefaction heavy organics grind into powder, the product of hydrophily first is obtained by hydroxylating, Carboxylation or sulfonation；(2) mixture of the first product and formaldehyde and thiocarbamide is reacted to obtain nitrogenous, sulphur the second product；(3) by the second product and a certain proportion of magnesium source mechanical mixture, then it is positioned in retort and carbonizes, obtains magnesia and the porous carbon mixture of nitrogen sulphur codope；Magnesia, which is removed, through pickling obtains nitrogen sulphur codope porous charcoal.It is contemplated that widening nitrogen containing species, sulfur containing species and the selection containing carbon matrix precursor when preparing nitrogen sulphur codope porous charcoal, while new way is found for the utilization of coal liquefaction residue；Nitrogen sulphur codope porous charcoal prepared by the present invention has excellent chemical property, is a kind of high performance electrode material for super capacitor and oxygen reduction reaction catalyst.
Description
Technical field
The present invention relates to a kind of nitrogen sulphur codope porous charcoal using the organic point of preparation of DCL/Direct coal liquefaction heavy and its preparation
Methods and applications.
Background technology
The energy characteristics in China few gas rich in coal and poor in oil, this just determines the energy resource structure feature in China necessarily based on coal
Body.Coal liquefaction is to alleviate the important channel of oil pressure, abundant and cheap coal resources using abundant coal resources
It is the important prerequisite that China can take the lead in using this technology.But no matter which kind of DCL/Direct coal liquefaction and isolation technics are used at present,
Inevitably produce the liquefied residue for accounting for raw coal total amount more than 20~30%, resource of the substantial amounts of residue to liquefaction process
Utilization rate and economy have immeasurable influence.Therefore, the high-effective classifying integrated utilization research of coal directly-liquefied residue is thing
Close a problem of direct coal liquefaction technology development.
Coal hydroliquefaction residue is the material of a kind of high-carbon, high ash and high-sulfur, and its main component is coal organism, coal has
Inorganic mineral and additional remaining deliquescence accelerant for being carried secretly in body etc..The utilization ways of liquefied residue mainly include gas
Change, burning and coking etc..At present, the main Land use systems of coal liquefaction residue are burnings, and this is not only a kind of greatly waste, and
And in residue sulphur comparision contents it is high, atmosphere pollution can be caused by being directly used in burning, and this runs counter to the original intention of clean coal technology.
Nitrogen sulphur codope porous charcoal is because the characteristics such as its special surface nature are in electro-catalysis and electrode of super capacitor material
The fields such as material show larger application potential, receive the extensive concern of researcher.Generally, nitrogen sulphur codope porous charcoal is prepared
Method be that nitrogenous and sulphur presoma is activated or template pore-creating obtains nitrogen sulphur codope porous charcoal, conventional presoma
Main organic matter, ionic liquid and the polymer substance higher including carbon amounts etc..Minhua Cao etc. then employ it is nitrogenous and
The ionic liquid of sulphur is prepared for specific surface area and is up to 1056m2g-1Nitrogen sulphur codope porous charcoal, resulting materials are that a kind of performance is excellent
Different oxygen reduction reaction catalyst.[Journal of Power Sources, 2014,259,138-144].CN 104108698
A discloses one kind, and using nitrogen-rich organic thing dimethylglyoxime as carbon source and nitrogen source, sulfuric acid is catalyst and sulphur source, dimethylglyoxime and first
Reaction product of the aldehyde under sulfuric acid catalysis is presoma, uses mesoporous silica molecular sieve SBA-15 to pass through dipping for template
Method combination high temperature pyrolysis technology prepares the nitrogen sulphur codope ordered mesoporous carbon with the hexagonal mesoporous structure of two dimension；Prepared nitrogen sulphur is total to
Doping ordered mesoporous carbon has high Heteroatom doping amount.The A of CN 104555987 disclose a kind of carboxyl by amino acid with
Sulfur-containing compound and nitrogen-containing compound are more effectively incorporated in together by the chemical reaction of amino and hydroxyl in chitosan molecule chain
The preparation method of nitrogen sulphur codope porous carbon material in one material, resulting materials are a kind of excellent electrode of super capacitor materials
Material.But majority is using the simultaneously nitrogenous and high molecular polymer of sulphur as presoma in the preparation process of nitrogen sulphur codope porous charcoal,
Cost is higher, and nitrogen source and sulphur source range of choice are limited.
The content of the invention
The present invention is intended to provide a kind of utilize organic point of method for preparing nitrogen sulphur codope porous charcoal of DCL/Direct coal liquefaction heavy.
Organic point of DCL/Direct coal liquefaction heavy has the characteristics that carbon content is high, is prone to polymerize or is crosslinked, and it is excellent to prepare Carbon Materials
Presoma.The present invention is divided into the reaction such as raw material, hydrophilized and polycondensation so that DCL/Direct coal liquefaction heavy is organic, passes through carbonization process
In-situ preparation magnesium oxide template, nitrogen sulphur codope porous carbon material is prepared, it is used as electrode material for super capacitor and oxygen also
Excellent performance is shown during former catalysts.This invents the selection model for having widened presoma and nitrogen containing species and sulfur containing species
Enclose, enrich the preparation technology of nitrogen sulphur codope porous charcoal, while be coal directly-liquefied residue as new energy electrode material
One new way of offer is efficiently provided.
Coal directly-liquefied residue is mainly by inorganic mineral, extra catalyst, together with the partial liquefaction mink cell focus being entrained with, and
Asphaltene and preasphaltene etc. form.In the present invention, DCL/Direct coal liquefaction heavy is organic be divided into caused by coal liquefaction except ash content,
Organic component outside light-end products, such as asphaltene, preasphaltene etc..
It is of the present invention with DCL/Direct coal liquefaction heavy it is organic be divided into raw material and prepare the method for nitrogen sulphur codope porous charcoal include：
(1) by organic point of grind into powder of DCL/Direct coal liquefaction heavy, hydrophily is obtained by hydroxylating, Carboxylation or sulfonation
First product；
(2) mixture of the first product and formaldehyde and thiocarbamide is reacted to obtain nitrogenous, sulphur the second product；
(3) by the second product and a certain proportion of magnesium source mechanical mixture, then it is positioned in retort and carbonizes, aoxidized
Magnesium and the porous carbon mixture of nitrogen sulphur codope；Magnesia, which is removed, through pickling obtains nitrogen sulphur codope porous charcoal.
Organic point of DCL/Direct coal liquefaction heavy is prepared as follows described in step (1) of the present invention：DCL/Direct coal liquefaction is residual
After ground-slag is broken, is extracted with organic solvent to organic solvent true qualities, be evaporated under reduced pressure and remove organic solvent in extract, it is direct to produce coal
Liquefy organic point of heavy.Wherein, organic solvent be selected from n-hexane, tetrahydrofuran, toluene, furfural, N, dinethylformamide, N,
N- dimethyl acetamides, ethylenediamine, quinoline, liquefied light oil and mink cell focus at least one.According to the one of the inventive method
Preferred embodiment, the particle diameter of organic point of DCL/Direct coal liquefaction heavy after grinding in step (1) are less than 150um, preferably 100~
150um。
First product preparation method is described in step (1) of the present invention, by organic point of DCL/Direct coal liquefaction heavy and H2O2, nitre
After acid or sulfonating agent are well mixed, 40 DEG C under inert atmosphere conditions~180 DEG C 1~24h of reaction, respectively obtain through perhydroxyl radical
Change, Carboxylation or sulfonation organic point of hydrophily DCL/Direct coal liquefaction heavy.The H2O2, nitric acid or sulfonating agent and DCL/Direct coal liquefaction
The mass ratio that organic point of heavy is 12：1~20：1；A kind of institute of the sulfonating agent in the concentrated sulfuric acid, chlorosulfonic acid, oleum
It is 90~98wt.% to state concentrated sulfuric acid concentration；Sulfur trioxide content is 15~50wt.% in the oleum；Preferably
The 98wt.% concentrated sulfuric acids；
The inert atmosphere is one kind in nitrogen, argon gas, helium, and inert gas flow is 50~300mL min-1。
According to the inventive method preferred embodiment, in step (1) of the present invention, sulfonating agent and DCL/Direct coal liquefaction weight
The mass ratio that organic point of matter is preferably 14：1~18：1；Reaction time is preferably 12~18h.Reaction temperature is preferably 120 DEG C
~160 DEG C；Atmosphere used is one kind in nitrogen, argon gas, helium, and inert gas flow is 50~300mL min-1。
According to the preferred scheme of the present invention, in step (2) of the present invention, the first product and formaldehyde and compound
Reactions steps are:First product is added into the saturated solution of thiocarbamide, the mass ratio of the first product and thiocarbamide is 0.5：1~
1.5：1；The mass ratio of the formalin that addition concentration is 5~37wt.% after well mixed, formalin and thiocarbamide is 1.5：1
~5.5：1；The reaction condition is to react 1min~1h at 50~150 DEG C, and moisture removal is removed in drying afterwards, you can obtains the second production
Thing.
According to the inventive method preferred embodiment, magnesium source is magnesia, magnesium carbonate, nitre in the step (3)
One kind in sour magnesium, magnesium sulfate, magnesium hydroxide, magnesium acetate, magnesium oxalate, magnesium citrate, magnesium chloride, more preferably citric acid
Magnesium, magnesium source are 1 with third product mass ratio：1~9：1；Charing process condition is in the step (3)：Heating schedule：Room temperature is extremely
400~550 DEG C, preferably 490 DEG C, 1~10 DEG C of min of heating rate-1, it is incubated 30min~3h；490 DEG C, to charing final temperature, heat up
1~10 DEG C of min of speed-1；Carbonize 600~1100 DEG C of final temperature, 0.5~10h of constant temperature time；The inert gas is nitrogen, argon gas
Or one kind in helium, inert gas flow are 50~300mL min-1。
According to the inventive method preferred embodiment, pickling described in step (3) removes the operation bar of magnesia
Part is：At room temperature, feed the mixture into and more than 24h is continuously stirred in the beaker containing hydrochloric acid solution, filter, filter cake is washed with water
To filtrate close to neutrality, then 5~20h, preferably 12h will be dried at 100~120 DEG C of filter cake.Concentration of hydrochloric acid solution used is
1mol/L；The mass ratio of the hydrochloric acid solution and mixture thing is 300~400：1.
The present invention is provided with above-mentioned nitrogen sulphur codope porous charcoal answering in ultracapacitor and oxygen reduction reaction catalyst
With.
Invention beneficial effect
(1) it is contemplated that widening when preparing nitrogen sulphur codope porous charcoal nitrogen containing species, sulfur containing species and containing carbon matrix precursor
Selection, while find new way for the utilization of coal liquefaction residue.
(2) nitrogen sulphur codope porous charcoal prepared by the present invention has excellent chemical property, is a kind of high performance super
Level capacitor electrode material.
(3) nitrogen sulphur codope porous charcoal prepared by the present invention has excellent electrocatalysis characteristic, is a kind of oxygen of high activity
Reduction catalyst.
Brief description of the drawings
Fig. 1 is the SEM photograph of the gained nitrogen sulphur codope porous charcoal of embodiment 1, shows the microstructure of porous charcoal.
Fig. 2 is nitrogen adsorption/desorption curve of the gained nitrogen sulphur codope porous charcoal of embodiment 1, shows the nitrogen of porous charcoal
Adsorpting characteristic.
Fig. 3 is the DFT pore size distribution curves of the gained nitrogen sulphur codope porous charcoal of embodiment 1, shows the hole size of porous charcoal
And distribution.
Fig. 4 is embodiment 4, embodiment 5, embodiment 6 and the gained nitrogen sulphur codope porous charcoal of embodiment 7 in 1MH2SO4Electrolysis
Liquid, 2mV s-1Under cyclic voltammetry curve.
Fig. 5 is the gained nitrogen sulphur codope porous charcoal of embodiment 4 in 1M H2SO4Constant current charge-discharge curve under electrolyte.
Fig. 6 is embodiment 4, embodiment 5, embodiment 6 and the gained nitrogen sulphur codope porous charcoal of embodiment 7 in 1MH2SO4Electrolysis
Quality specific capacitance under liquid is with current density change graph of a relation.
Fig. 7 is embodiment 1, embodiment 2, embodiment 3 and the gained nitrogen sulphur codope porous charcoal of embodiment 8 in oxygen saturation
Linear voltammetric scan figure under 0.1M KOH electrolyte.
Embodiment
Utilization DCL/Direct coal liquefaction heavy provided by the present invention, which is described in further detail, below by specific embodiment has
The method that machine point prepares nitrogen sulphur codope porous charcoal, but following embodiments are only used for explaining the present invention, rather than for limiting this
The scope of invention.
In the present invention, the organic organic component being divided into coal directly-liquefied residue in addition to ash content of DCL/Direct coal liquefaction heavy,
Mainly include asphaltene, preasphaltene etc..Its preparation method is：After coal directly-liquefied residue is crushed, with organic solvent tetrahydrochysene
Furans is extracted to organic solvent true qualities, is evaporated under reduced pressure and is removed organic solvent in extract, by gained solids be ground to 100um with
Under produce organic point of DCL/Direct coal liquefaction heavy.
But also do not limit this method.
Embodiment 1
Organic point of DCL/Direct coal liquefaction heavy after 10g the is ground sulfonation 15h at 100 DEG C in 200 gram of 90% concentrated sulfuric acid, is obtained
To hydrophilic first product.The products of 0.5g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1g, Zhi Houjia
Enter 5.5g formalins (37wt%), after 100 DEG C are reacted 10min, go moisture removal to obtain the second product in 100 DEG C of dryings.Take
Second product 1g and 5g magnesium citrate mechanical mixtures, are placed in retort, in 200mL min-1Ar atmosphere under, with 2 DEG C
min-1Speed from room temperature to 490 DEG C, be incubated 1h, afterwards again with 5 DEG C of min-1Speed be warming up to 700 DEG C from 490 DEG C,
Be incubated 1h, after in 200mL min-1Ar atmosphere under be cooled to room temperature, gained mixture washs through 1M HCl and removes magnesia, mistake
Filter, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal, the master of the material through 100 DEG C to filtrate close to neutrality, filter cake
Want property as shown in table 1.
Embodiment 2
Organic point of DCL/Direct coal liquefaction heavy after 10g the is ground sulfonation 1h at 180 DEG C in 200 gram of 98% concentrated sulfuric acid, is obtained
To hydrophilic first product.The products of 1.5g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1g, Zhi Houjia
Enter 1.5g formalins (37wt%), after 150 DEG C are reacted 1min, go moisture removal to obtain the second product in 100 DEG C of dryings.Take
Two product 1g and 6g magnesium oxalates (or magnesium citrate) mechanical mixture, are placed in retort, in 200mL min-1Ar atmosphere
Under, with 2 DEG C of min-1Speed from room temperature to 490 DEG C, be incubated 30min, afterwards again with 5 DEG C of min-1Speed risen from 490 DEG C
Temperature to 800 DEG C, be incubated 7h, after in 200mLmin-1Ar atmosphere under be cooled to room temperature, gained mixture is washed through 1M HCl and removed
Magnesia, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal through 100 DEG C to filtrate close to neutrality, filter cake, should
The main character of material is as shown in table 1.
Embodiment 3
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is in 180 grams of oleum (15wt%SO3) in sulphur at 40 DEG C
Change 24h, obtain hydrophilic first product.The products of 1g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1g,
4g formalins (37wt%) are added afterwards, after 50 DEG C are reacted 1h, go moisture removal to obtain the second product in 100 DEG C of dryings.Take
Second product 1g and 5g magnesium citrate mechanical mixtures, are placed in retort, in 200mL min-1Nitrogen atmosphere under, with 1
℃min-1Speed from room temperature to 490 DEG C, be incubated 1h, afterwards again with 5 DEG C of min-1Speed be warming up to 900 from 490 DEG C
DEG C, be incubated 3h, after in 200mL min-1Nitrogen atmosphere under be cooled to room temperature, gained mixture removes deoxidation through 1M HCl washings
Magnesium, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal, the material through 100 DEG C to filtrate close to neutrality, filter cake
Main character it is as shown in table 1.
Embodiment 4
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is in 180 grams of oleum (50wt%SO3) in sulphur at 40 DEG C
Change 15h, obtain hydrophilic first product.The products of 1g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1g,
4g formalins (37wt%) are added afterwards, after 100 DEG C are reacted 10min, go moisture removal to obtain the second production in 100 DEG C of dryings
Thing.The second product 1g and 5g magnesium chloride mechanical mixtures are taken, is placed in retort, in 50mL min-1Helium atmosphere under, with
10℃min-1Speed from room temperature to 400 DEG C, be incubated 1h, afterwards again with 5 DEG C of min-1Speed be warming up to 700 from 400 DEG C
DEG C, be incubated 1h, after in 50mL min-1Helium atmosphere under be cooled to room temperature, gained mixture removes deoxidation through 1M HCl washings
Magnesium, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal, the material through 100 DEG C to filtrate close to neutrality, filter cake
Main character it is as shown in table 1.
Embodiment 5
Organic point of DCL/Direct coal liquefaction heavy after 10g the is ground sulfonation 15h at 100 DEG C in 120 gram of 98% concentrated sulfuric acid, is obtained
To hydrophilic first product.The products of 1g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1.5g, Zhi Houjia
Enter 4g formalins (37wt%), after 100 DEG C are reacted 30min, go moisture removal to obtain the second product in 100 DEG C of dryings.Take
Two product 1g and 4g magnesium acetates (or magnesium oxalate) mechanical mixture, are placed in retort, in 200mL min-1Ar atmosphere under,
With 2 DEG C of min-1Speed from room temperature to 400 DEG C, be incubated 1h, afterwards again with 1 DEG C of min-1Speed be warming up to from 400 DEG C
600 DEG C, be incubated 10h, after in 200mL min-1Ar atmosphere under be cooled to room temperature, gained mixture is through 1M HCl washings except deoxidation
Change magnesium, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal, the material through 100 DEG C to filtrate close to neutrality, filter cake
The main character of material is as shown in table 1.
Embodiment 6
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground is added into 200 grams of 30wt% hydrogenperoxide steam generator,
40 DEG C of backflow 4h, 70 DEG C of backflow 12h, are dried to obtain the first product afterwards.It is 1g's to take the products of 1g first to add to thiocarbamide content
In the saturated solution of thiocarbamide, 4g formalins (37wt%) are added afterwards, after 100 DEG C are reacted 10min, are gone in 100 DEG C of dryings
Moisture removal obtains the second product.The second product 1g and 9g magnesium hydroxide mechanical mixtures are taken, is placed in retort, in 200mL
min-1Ar atmosphere under, with 1 DEG C of min-1Speed from room temperature to 490 DEG C, be incubated 1h, afterwards again with 5 DEG C of min-1Speed
Be warming up to 700 DEG C from 490 DEG C, be incubated 1h, after in 200mL min-1Ar atmosphere under be cooled to room temperature, gained mixture is through 1M
HCl washings remove magnesia, filtering, filter cake are washed with water and is drying to obtain nitrogen sulphur to filtrate close to neutrality, filter cake through 100 DEG C and is co-doped with
Miscellaneous porous charcoal.
Embodiment 7
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground adds 40 DEG C of sulfonation 10h into 120 grams of chlorosulfonic acids, through water
Wash, be dried to obtain the first product.The products of 1g first are taken to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1.5g, Zhi Houjia
Enter 3g formalins (37wt%), after 100 DEG C are reacted 10min, go moisture removal to obtain the second product in 100 DEG C of dryings.Take
Two product 1g and 7g magnesium nitrates (or magnesium sulfate) mechanical mixture, are placed in retort, in 200mL min-1Ar atmosphere under,
With 2 DEG C of min-1Speed from room temperature to 550 DEG C, be incubated 1h, afterwards again with 5 DEG C of min-1Speed be warming up to from 550 DEG C
700 DEG C, be incubated 1h, after in 300mL min-1Nitrogen atmosphere under be cooled to room temperature, gained mixture is washed through 1M HCl and removed
Magnesia, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal through 100 DEG C to filtrate close to neutrality, filter cake.
Embodiment 8
Organic point of DCL/Direct coal liquefaction heavy after 10g is ground adds 80 DEG C of oxidationization 4h into 200 grams of concentrated nitric acids, through water
Wash, be dried to obtain the first product.Take the products of 1g first to add into the saturated solution for the thiocarbamide that thiocarbamide content is 1g, add afterwards
4g formalins (37wt%), after 100 DEG C are reacted 20min, moisture removal is gone to obtain the second product in 100 DEG C of dryings.Take second
Product 1g and 1g magnesia (or magnesium carbonate) mechanical mixture, are placed in retort, in 200mL min-1Ar atmosphere under, with
5℃min-1Speed from room temperature to 490 DEG C, be incubated 3h, afterwards again with 10 DEG C of min-1Speed be warming up to from 490 DEG C
1100 DEG C, be incubated 0.5h, after in 200mLmin-1Ar atmosphere under be cooled to room temperature, gained mixture is washed through 1M HCl and removed
Magnesia, filtering, filter cake is washed with water and is drying to obtain nitrogen sulphur codope porous charcoal through 100 DEG C to filtrate close to neutrality, filter cake.
Comparative example 1
Take 1g melamines to be dissolved in 6mL formalins, sodium hydroxide regulation pH to 8,60 DEG C of water-bath 30min, must clarify
Solution A；1g coal directly-liquefied residue heavy organics are taken to be dissolved in 25mL tetrahydrofurans, and by coal tar pitch and magnesium citrate quality
Than for 1:3 add magnesium citrate, are sufficiently mixed uniformly, obtain mixed liquid B；Solution A is mixed with mixed liquid B, 80 DEG C of reaction time
For 5h, make its full cross-linked blending, residual solvent in gained blend is evaporated, through 150 DEG C of solidification 12h；In retort,
Under 50mL/min helium atmosphere, 700 DEG C are warming up to 1 DEG C/min heating rate, 5h is carbonized, is washed through pickling, after drying,
Produce N doping porous charcoal.
Application examples 1
By sample, conductive black and the polytetrafluoroethylene (PTFE) of embodiment 4,5,6 or 7 with 80:10:10 mass ratio is scattered in few
Measure in ethanol, after ultrasonic mixing, it is about 8mm disks that roll-in slabbing, which is cut into diameter, by 100 DEG C of drying for standby, from wherein
Quality is tested between 4.5~5.5mg electrode slice.Electrode slice is placed in stainless (steel) wire and is fabricated to working electrode.Utilize
The chemical property of electrochemical workstation CHI660C test materials, method of testing is cyclic voltammetry, chronoptentiometry, according to
Formula C=(I Δs t)/(m Δ V), calculates the specific capacitance value of material.Test uses three-electrode system：The carbon resistance rod of preparation is work
Electrode, Pt electrodes are to electrode, Hg/Hg2SO4Electrode is reference electrode, and voltage range -0.7~0.3V, electrolyte is 1mol L-1H2SO4Solution.There are certain redox peaks in the cyclic voltammetry curve shown in Fig. 4, show that material has fake capacitance.
The constant current charge-discharge curve symmetry that the chronoptentiometry of embodiment illustrated in fig. 54 measures well illustrates that material invertibity is preferable, but by
Cause curve to deviate isosceles triangle to a certain degree in the presence of redox reaction, while also illustrate the presence of fake capacitance.
As can be seen from Figure 6 in 100mA g-1The specific capacitance value of material is 180~296F g under current density-1；When current density increases
To 2A g-1When, the capacity retention of embodiment 4 shows that this material has good multiplying power property up to 76%.
Application examples 2
In the present invention, repaiied respectively with embodiment 1, embodiment 2, embodiment 3 and the gained nitrogen sulphur codope porous charcoal of embodiment 8
The glass-carbon electrode (diameter about 5mm) of decorations is reference electrode as working electrode, Ag/AgCl (sat.), and platinum filament (Pt) is auxiliary electricity
Pole, the electrocatalysis characteristic of porous charcoal is tested using linear voltammetric scan.The specific preparation process of working electrode is as follows：Preparation work
Before electrode, glassy carbon electrode surface is polished to minute surface with 1.0,0.05 and 0.03 μm of gamma oxidation aluminium powder successively, then uses distilled water
Clean up and vacuum drying is standby.4mg catalyst is taken in sample bottle, sequentially adds 785uL absolute ethyl alcohols, 200uL go from
Sub- water, 15uL Nafion (10%wt), ultrasonic half an hour finely dispersed suspension derived above, 10uL suspensions is taken afterwards
Drop to glassy carbon electrode surface (204ug cm-2), dry at room temperature standby.Electrolyte during test is the 0.1M KOH of oxygen saturation
Solution, potential range are respectively 0.2~-1.0V, and sweep speed is 10mV s-1, test temperature is room temperature, and Fig. 7 is that gained is linear
Voltammetric scan test result, and the linear voltammetric scan test result of attached business 20%Pt/C catalyst.
The composition and pore structure parameter of the nitrogen sulphur codope porous charcoal of table 1
Claims (7)
1. a kind of utilize organic point of method for preparing nitrogen sulphur codope porous charcoal of DCL/Direct coal liquefaction heavy, it is characterised in that described
Method comprises the following steps：
(1) by organic point of grind into powder of DCL/Direct coal liquefaction heavy, hydrophily is obtained by hydroxylating or Carboxylation or sulfonation
One product；
(2) mixture of the first product and formaldehyde and thiocarbamide is reacted to obtain nitrogenous, sulphur the second product；
(3) by the second product and a certain proportion of magnesium source mechanical mixture, it is placed in retort and carbonizes, obtains magnesia and be total to nitrogen sulphur
Adulterate porous carbon mixture；Magnesia, which is removed, through pickling obtains nitrogen sulphur codope porous charcoal.
2. according to the method for claim 1, it is characterised in that in the step (1), organic point of DCL/Direct coal liquefaction heavy with
H2O2Or after nitric acid or sulfonating agent are well mixed, 40 DEG C~180 DEG C 1~24h of reaction, respectively obtain by hydroxylating, it is Carboxylation or
Organic point of the hydrophily heavy of sulfonation；
The H2O2Or nitric acid or the mass ratio of sulfonating agent and organic point of DCL/Direct coal liquefaction heavy are 12：1~20：1；
The one kind of the sulfonating agent in the concentrated sulfuric acid, chlorosulfonic acid, oleum, the concentrated sulfuric acid concentration are 90~98wt.%；
Sulfur trioxide content is 15~50wt.% in the oleum.
3. according to the method for claim 1, it is characterised in that in the step (2), the first product mixes with formaldehyde and thiocarbamide
The reactions steps of compound are:First product is added into the saturated solution of thiocarbamide, the mass ratio of the first product and thiocarbamide is
0.5：1~1.5：1；The mass ratio of the formalin that concentration is 5~37wt.%, formalin and thiocarbamide is added after well mixed
For 1.5：1~5.5：1；The reaction condition is to react 1min~1h at 50~150 DEG C, and moisture removal is removed in drying afterwards, you can
To the second product.
4. according to the method for claim 1, it is characterised in that in the step (3) magnesium source be selected from magnesia, magnesium carbonate,
One kind in magnesium nitrate, magnesium sulfate, magnesium hydroxide, magnesium acetate, magnesium oxalate, magnesium citrate, magnesium chloride；
The mass ratio of magnesium source and the second product is 1：1~9：1.
5. according to the method for claim 1, it is characterised in that charing process condition is in the step (3)：Heat up journey
Sequence：For room temperature to 400~550 DEG C, heating rate is 1~10 DEG C of min-1, after being incubated 30min~3h；600~1100 DEG C are warming up to,
1~10 DEG C of min of heating rate-1, 0.5~10h of constant temperature；
For charing process in inert gas, the inert gas is one kind in nitrogen, argon gas or helium, and inert gas flow is
50~300mL min-1。
6. the nitrogen sulphur codope porous charcoal prepared such as Claims 1 to 5 any one methods described.
7. nitrogen sulphur codope porous charcoal as claimed in claim 6 is urged as electrode material for super capacitor and oxygen reduction reaction
Application in agent.
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| CN107098343A (en) * | 2017-05-31 | 2017-08-29 | 华南理工大学 | A kind of CaCl2Gu the method that sulphur prepares nitrogen sulphur codope porous carbon materials |
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| CN111807344B (en) * | 2020-06-17 | 2023-03-03 | 中国石油大学(华东) | Doped porous carbon based on coal/heavy oil hydrogenation co-refining residues and application thereof |
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