CN109608410A - A kind of preparation method of high-specific surface area multilevel structure melamine - Google Patents
A kind of preparation method of high-specific surface area multilevel structure melamine Download PDFInfo
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- CN109608410A CN109608410A CN201910083026.XA CN201910083026A CN109608410A CN 109608410 A CN109608410 A CN 109608410A CN 201910083026 A CN201910083026 A CN 201910083026A CN 109608410 A CN109608410 A CN 109608410A
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- melamine
- preparation
- specific surface
- surface area
- acid
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 Fig. 1 (a) is shown Natural products 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNMCQEMQGJHTQF-UHFFFAOYSA-N 3,5,6,7-tetrahydrotetrazolo[1,5-b][1,2,4]triazine Chemical compound N1CCN=C2N=NNN21 RNMCQEMQGJHTQF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/56—Preparation of melamine
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of high-specific surface area multilevel structure melamine, the step of preparation method, is as follows: being first dispersed in melamine powder in the mixed solution of pure and mild acid, then dispersion liquid is stirred, to get high-specific surface area multilevel structure melamine after being filtered, washed and dried drying.The method is low for equipment requirements, easy to operate, and filtrate is reusable.Compared with general goods melamine powder, high-specific surface area multilevel structure melamine obtained by this method contains a large amount of mesoporous, its specific surface area increases more than 40 times, is worth in the fields such as the preparation of graphite phase carbon nitride based photocatalyst, fire-retardant with major application.
Description
Technical field
The present invention relates to a kind of preparation methods of high-specific surface area multilevel structure melamine, belong to functional non-metallic material
Expect technical field.
Background technique
Melamine (C3H6N6) it is commonly called as melamine, melamine, extract of protein and cyanuramide, it is important urea post-processing
Product, and a kind of important Organic Chemicals.The yield of domestic product melamine in 2017 about at 115.59 ten thousand tons, at
For the maximum Melamine Production base in the whole world.Melamine thermal stability with higher, anti-flammability, waterproofness and excellent
Mechanical performance and resistance to ag(e)ing etc. are widely used in timber, plastics, coating, papermaking, weaving, leather, medicine, building and light
The fields such as work, in addition, melamine can also make polymerization inhibitor, water-reducing agent, glass fiber binder, formaldehyde cleaning agent etc..In recent years,
Melamine is further taken seriously as visible light catalyst graphite phase carbon nitride (CN) most cheap raw material is prepared, but institute
Prepare that CN specific surface area is extremely low, and photocatalysis performance is poor, the self structure of melamine is one of the reason of causing this phenomenon.
Chinese patent literature CN105597803A discloses a kind of mesoporous carbon nitride photocatalyst and preparation method thereof, is mainly characterized by
Using mesoporous carbon be template prepare mesoporous carbonitride, can simply easy removed template method, and on the mesoporous carbonitride of preparation influence
It is smaller, mesoporous carbonitride specific surface area with higher.Preparation step are as follows: 1. polyether type polymer is template, with β-ring paste
Essence is carbon source, obtains mesoporous carbon by low temperature polymerization, high-temperature calcination；2. being template, Gao Wenre using 1. prepared mesoporous carbon
After polymeric melamines, the empty carbon template that is situated between is removed, the mesoporous carbonitride of high-specific surface area is made.This method simple process, cost
It is cheap, the mesoporous carbon nitride photocatalyst visible light catalysis activity with higher of preparation.The prior art mainly to carbon source into
Row transformation, prepares mesoporous carbon, and mesoporous carbon is recycled to prepare the mesoporous carbonitride of high-specific surface area, but the transformation to melamine
But it is rarely reported.
Currently, general goods melamine powder is mainly made of tens microns of bulky grain, it is non-porous structure.In recent years
Though the melamine sponge of rise is porous structure, predominantly macropore, almost without mesoporous presence, and the uniqueness of mesoporous material
Matter is obvious to all.Therefore, application of the mesoporous melamine in the fields such as fire-retardant, building and CN preparation is urgently explored, and is ground
The technology of preparing for sending out melamine mesoporous just seems especially urgent.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation sides of high-specific surface area multilevel structure melamine
Method, this method simple process, low in cost, the multilevel structure melamine of preparation contains a large amount of mesoporous, has high specific surface
Product is more than 40 times of general goods melamine powder.
Technical scheme is as follows:
A kind of preparation method of high-specific surface area multilevel structure melamine, steps are as follows:
(1) melamine powder is dispersed with stirring in the mixed solution of pure and mild acid, obtains dispersion liquid；
(2) dispersion liquid in step (1) is stirred under 10~80 DEG C of whipping temp, mixing time be 1~for 24 hours；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), to get high-specific surface area after washing, drying through alcohol
Multilevel structure melamine.
Preferred according to the present invention, melamine powder described in step (1) is ordinary commercial products；Preferably, step
(1) melamine powder described in is purchased from Sinopharm Chemical Reagent Co., Ltd., article No. 30112528.
Preferred according to the present invention, alcohol described in step (1) and (3) is anhydrous methanol, dehydrated alcohol, ethylene glycol, third
The mixing of one or more of glycol, glycerol；Preferably, the alcohol is dehydrated alcohol.
Preferred according to the present invention, acid described in step (1) is concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid, dense formic acid or dense secondary
The mixing of one or more of chloric acid；Preferably, the acid is one of concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid；Further
Preferably, the acid is concentrated hydrochloric acid.
It is further preferred that the mass concentration of the concentrated hydrochloric acid is 36-38%, the mass concentration of the concentrated nitric acid is 21-
23%, the mass concentration of the concentrated phosphoric acid is 83-87%, and the mass concentration of the dense formic acid is 87-89%, the dense hypochlorous acid
Mass concentration be 10-13%.
Preferred according to the present invention, the volume ratio of acid described in step (1) and alcohol is 1:(2-50)；Preferably, described
Acid and the volume ratio of alcohol be 1:10.
It is preferred according to the present invention, concentration of the melamine powder in dispersion liquid described in step (1) is 0.01~
0.20g/mL, it is preferred that concentration of the melamine powder in dispersion liquid is 0.10g/mL.
Preferred according to the present invention, whipping temp described in step (2) is 25 DEG C.
Preferred according to the present invention, mixing time described in step (2) is 2h.
It is preferred according to the present invention, drying described in step (3) be 50~100 DEG C dry 5~for 24 hours；Preferably, institute
The drying stated is in 60 DEG C of dry 12h.
Preferred according to the present invention, drying described in step (3) carries out in air dry oven.
Technical characterstic of the invention is as follows:
One, during the present invention prepares high-specific surface area multilevel structure melamine, acid described in step (1) with
The volume ratio of alcohol is 1:(2-50)；Preferably, the volume ratio of the acid and alcohol is 1:10.Present inventors have unexpectedly found that preparing
During high-specific surface area multilevel structure melamine, acid is very important with the ratio of alcohol, when ratio is excessively high, can introduce a large amount of
Water influences melamine salt solubility, is unfavorable for the formation of multilevel structure.Also it is unfavorable for the shape of multilevel structure when ratio is too low
At.
Two, the present invention makes up for the shortcomings of the prior art, is successfully prepared high-specific surface area multilevel structure melamine.This
Inventor has been surprisingly found that in studying for a long period of time, melamine and acid formed melamine hydrochlorate (acid is strong acid) or melamine/
Sour bond complexes (acid is weak acid), and this hydrochlorate or bond complexes can be slightly soluble in alcohol.This dissolution, the dynamic being precipitated
Equilibrium process " can cut " melamine, to form multilevel structure.
Beneficial effects of the present invention are as follows:
1, compared with general goods melamine powder, high-specific surface area multilevel structure melamine prepared by the present invention
Containing a large amount of mesoporous, there is high specific surface area and pore volume, and only need customary acid to carry out room temperature processing and can be obtained, prepare
Process is simple, and required device simple, energy consumption is small, at low cost, it is easy to accomplish industrialized production.
2, it is reusable to prepare the filtrate generated during high-specific surface area multilevel structure melamine by the present invention, not only
It reduces costs, and reduces discharge of wastewater, meet cheap, environmentally friendly requirement.
3, by high-specific surface area multilevel structure melamine prepared by the present invention because its specific surface area is higher, it is fire-retardant,
The fields such as melamine foam and CN preparation have great application value.
Detailed description of the invention
Fig. 1 is the SEM photograph of melamine sample；
In figure, (a) is the SEM photograph of general goods melamine powder；(b) alcohol prepared for comparative example 1 changes melamine
The SEM photograph of amine；(c) SEM photograph of the melamine prepared for embodiment 1；It (d) is the melamine of the preparation of embodiment 1
Partial enlargement SEM photograph；
Fig. 2 is the N of melamine prepared by general goods melamine powder and embodiment 12Adsorption desorption isothermal curve figure
With pore size distribution curve figure (illustration)；
In figure: MA refers to general goods melamine powder, and MAH refers to melamine prepared by embodiment 1；
The N for the MCN that Fig. 3 is CN prepared by comparative example 2 and prepared by experimental example 12Adsorption desorption isothermal curve figure；
The pore size distribution curve figure for the MCN that Fig. 4 is CN prepared by comparative example 2 and prepared by experimental example 1；
The MCN that Fig. 5 is CN prepared by comparative example 2 and prepared by experimental example 1 is under visible light to the degradation curve of rhodamine B
Figure.
Specific embodiment
Below with reference to specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited in
This.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Melamine powder is purchased from Sinopharm Chemical Reagent Co., Ltd., article No. 30112528.
In following embodiments, SEM photograph is obtained by the observation of Hitachi SU8010 type field emission scanning electron microscope；N2It inhales
Isothermal curve is desorbed to be measured by the full-automatic specific surface area of Kang Ta instrument company, U.S. Quadrasorb EVO type and Porosimetry,
Specific surface area is obtained by BET method, and pore size distribution curve carries out processing acquisition to adsorption line branch by using BJH method.
Embodiment 1
A kind of preparation method of high-specific surface area multilevel structure melamine, steps are as follows:
(1) 20mL dehydrated alcohol is mixed into obtain mixed solution with the concentrated hydrochloric acid solution that 1.55mL mass concentration is 36%, it will
2g melamine powder is dispersed with stirring in above-mentioned mixed solution, obtains dispersion liquid；
(2) dispersion liquid in step (1) is stirred under 25 DEG C of whipping temp, mixing time 2h；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), after dehydrated alcohol washs, in 60 DEG C of air blast
Dry 12h is in drying box to get high-specific surface area multilevel structure melamine.
Embodiment 2
A kind of preparation method of high-specific surface area multilevel structure melamine, steps are as follows:
(1) 20mL glycerol is mixed into obtain mixed solution with the concentrated phosphoric acid that 0.87mL mass concentration is 85%, by 2g tri-
Poly cyanamid powder is dispersed with stirring in above-mentioned mixed solution, obtains dispersion liquid；
(2) dispersion liquid in step (1) is stirred under 70 DEG C of whipping temp, mixing time 5h；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), after dehydrated alcohol washs, in 70 DEG C of air blast
Dry 10h is in drying box to get high-specific surface area multilevel structure melamine.
Embodiment 3
A kind of preparation method of high-specific surface area multilevel structure melamine, steps are as follows:
(1) by 20mL ethylene glycol and 10mL nitric acid solution, (3.2mL mass concentration is that 69% concentrated nitric acid is added to 6.8mL water
In) mixed solution is mixed to obtain, 2g melamine powder is dispersed with stirring in above-mentioned mixed solution, dispersion liquid is obtained；
(2) dispersion liquid in step (1) is stirred under 30 DEG C of whipping temp, mixing time 17h；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), after dehydrated alcohol washs, in 90 DEG C of air blast
Dry 6h is in drying box to get high-specific surface area multilevel structure melamine.
Comparative example 1
A kind of alcohol changes the preparation method of melamine, and steps are as follows:
(1) 2g melamine powder is dispersed with stirring in 20mL dehydrated alcohol, obtains dispersion liquid；
(2) dispersion liquid in step (1) is stirred under 25 DEG C of whipping temp, mixing time 2h；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), after dehydrated alcohol washs, in 60 DEG C of air blast
Dry 12h changes melamine to get alcohol in drying box.
The pattern of general goods melamine powder such as Fig. 1 (a) is shown, as can be seen from the figure general goods melamine
Powder is mainly made of tens microns of partial size of bulky grain；Alcohol prepared by comparative example 1 changes pattern such as Fig. 1 (b) institute of melamine
Show, it can be seen from the figure that alcohol prepared by comparative example 1, which changes melamine and general goods melamine powder, has similar figures
Looks, i.e. ethyl alcohol will not cause the pattern of general goods melamine powder to change.High-specific surface area multistage knot prepared by embodiment 1
Shown in the pattern of structure melamine such as Fig. 1 (c), shown in partial enlarged view such as Fig. 1 (d), it can be seen by Fig. 1 (a) and Fig. 1 (c)
Out, the bulky grain of general goods melamine powder be transformed to nanometer rods (or band) composition multilevel structure, medium rod (or
Band) it is several microns a length of, average diameter is dozens to a few hundred nanometers.Height prepared by general goods melamine powder and embodiment 1
The varying topography of specific surface area multilevel structure melamine has strongly suggested " cutting " effect of acid.
The N of high-specific surface area multilevel structure melamine prepared by general goods melamine powder and embodiment 12It inhales de-
Attached isothermal curve and pore size distribution curve as shown in Fig. 2, general goods melamine powder N2Adsorption desorption isothermal curve is without stagnant
Ring and its pore size distribution curve does not have peak afterwards, is shown to be non-porous structure, specific surface area and pore volume are respectively 0.28m2/ g and
3.9×10–5cm3/g.And the N of high-specific surface area multilevel structure melamine prepared by embodiment 12Adsorption desorption isothermal curve is IV
Type, and there is H3 type hysteresis loop, the mesoporous presence of slot type is shown, is coincide with Fig. 1 (c) SEM result, pore size distribution curve
Show mesoporous pore size mainly in 2~8nm.Embodiment 1 prepare high-specific surface area multilevel structure melamine specific surface area and
Pore volume is respectively 12.46m2/ g and 1.8 × 10–2cm3/ g compares general goods melamine powder and has increased separately about 44.5
Times and 460 times.
Experimental example 1
The high-specific surface area multilevel structure melamine that embodiment 1 is prepared is put into 20mL crucible and is placed in Muffle furnace
In, heating rate is set as 5 DEG C/min, is heated to 550 DEG C, keeps the temperature 4h, then cooled to room temperature, product is pulverized
End is denoted as MCN to get graphite phase carbon nitride.
Comparative example 2
2g general goods melamine powder is added in 20mL crucible, is placed in Muffle furnace, heating rate is set
For 5 DEG C/min, it is heated to 550 DEG C and keeps the temperature 4h, then cooled to room temperature, by product grind into powder to get graphite-phase
Carbonitride is denoted as CN.
Preparation graphite phase carbon nitride is an application of the melamine in photocatalysis field.MCN and right prepared by experimental example 1
The N of CN prepared by ratio 22Adsorption desorption isothermal curve is as shown in figure 3, its pore size distribution curve is as shown in Figure 4, the results showed that, CN
All there is IV type thermoisopleth and H3 type hysteresis loop, as meso-hole structure with MCN, the specific surface area and pore volume of CN are respectively
6.67m2/ g and 3.35 × 10–2cm3/ g, and that MCN is respectively 13.01m2/ g and 6.23 × 10–2cm3/ g, comparing CN has obvious increasing
Add, especially the pore size distribution curve of MCN shows new mesoporous generation, and pore diameter range is 2~6nm.
MCN prepared by experimental example 1 and CN prepared by comparative example 2 is applied to the degradation of rhodamine B (10mg/L), it is seen that light
The degradation rate of lower rhodamine B is as shown in Figure 5.As shown in Figure 5, rhodamine B itself is almost non-degradable, and MCN is to rhodamine B
Degradation rate is significantly greater than the degradation rate of CN, shows the high-specific surface area multilevel structure melamine prepared with embodiment 1
Carbonitride for raw material preparation has higher photocatalysis compared with the carbonitride prepared by raw material of general goods melamine powder
Activity.
Obviously, the above embodiment of the present invention and experimental example are only melamine simply answering in numerous application fields
With, it is intended to clearly illustrate popularity example of the invention, and be not to application field of the invention and embodiment party
The restriction of formula.For the concrete application of every field, other various forms of variations should be made in particular situations.Here it is not necessarily to
Also all embodiments can not be exhaustive.It is any modification done within the spirit and principles of the present invention, equivalent
Replacement and improvement etc., should all be included in the scope of protection of the claims of the present invention.
Claims (9)
1. a kind of preparation method of high-specific surface area multilevel structure melamine, steps are as follows:
(1) melamine powder is dispersed with stirring in the mixed solution of pure and mild acid, obtains dispersion liquid；
(2) dispersion liquid in step (1) is stirred under 10~80 DEG C of whipping temp, mixing time be 1~for 24 hours；
(3) precipitating is collected by filtration in the dispersion liquid after stirring in step (2), to get high-specific surface area multistage after washing, drying through alcohol
Structure melamine.
2. preparation method as described in claim 1, which is characterized in that alcohol described in step (1) and (3) be anhydrous methanol,
The mixing of one or more of dehydrated alcohol, ethylene glycol, propylene glycol, glycerol.
3. preparation method as described in claim 1, which is characterized in that acid described in step (1) be concentrated hydrochloric acid, concentrated nitric acid,
The mixing of one or more of concentrated phosphoric acid, dense formic acid or dense hypochlorous acid.
4. preparation method as claimed in claim 3, which is characterized in that the mass concentration of the concentrated hydrochloric acid is 36-38%, described
The mass concentration of concentrated nitric acid is 21-23%, and the mass concentration of the concentrated phosphoric acid is 83-87%, the mass concentration of the dense formic acid
For 87-89%, the dense hypochlorous mass concentration is 10-13%.
5. preparation method as described in claim 1, which is characterized in that the volume ratio of acid described in step (1) and alcohol is 1:
(2-50)。
6. preparation method as described in claim 1, which is characterized in that melamine powder described in step (1) is being dispersed
Concentration in liquid is 0.01~0.20g/mL.
7. preparation method as described in claim 1, which is characterized in that whipping temp described in step (2) is 25 DEG C.
8. preparation method as described in claim 1, which is characterized in that mixing time described in step (2) is 2h.
9. preparation method as described in claim 1, which is characterized in that drying described in step (3) is dry at 50~100 DEG C
Dry 5~for 24 hours.
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