CN109608410B - Preparation method of melamine with high specific surface area and multilevel structure - Google Patents
Preparation method of melamine with high specific surface area and multilevel structure Download PDFInfo
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- CN109608410B CN109608410B CN201910083026.XA CN201910083026A CN109608410B CN 109608410 B CN109608410 B CN 109608410B CN 201910083026 A CN201910083026 A CN 201910083026A CN 109608410 B CN109608410 B CN 109608410B
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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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 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 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 21
- 239000011941 photocatalyst Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000007605 air drying Methods 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
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 102000007327 Protamines Human genes 0.000 description 1
- 108010007568 Protamines Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
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- 239000013043 chemical agent Substances 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 melamine forms melamine salts Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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- 229940048914 protamine Drugs 0.000 description 1
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- 150000003839 salts Chemical group 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
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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
- 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
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- 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
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- Engineering & Computer Science (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a preparation method of melamine with a high specific surface area and a multilevel structure, which comprises the following steps: firstly, dispersing melamine powder in a mixed solution of alcohol and acid, then stirring the dispersion solution, and filtering, washing and drying to obtain the high-specific surface area multi-stage structure melamine. The method has low requirement on equipment, is simple to operate, and can recycle the filtrate. Compared with common commercial melamine powder, the high-specific surface area multi-stage structure melamine prepared by the method contains a large number of mesopores, the specific surface area of the melamine is increased by more than forty times, and the melamine has great application value in the fields of preparation of graphite phase carbon nitride based photocatalyst, flame retardance and the like.
Description
Technical Field
The invention relates to a preparation method of melamine with a high specific surface area and a multilevel structure, belonging to the technical field of functional non-metallic materials.
Background
Melamine (C)3H6N6) Commonly known as melamine, tripolyamide, protamine and cyanuramide, is an important post-processing product of urea and also an important organic chemical raw material. The yield of the melamine produced in China in 2017 is about 115.59 ten thousand tons, and the melamine production method becomes the largest global melamine production base. The melamine has higher thermal stability, flame retardance, waterproofness, excellent mechanical properties, aging resistance and the like, is widely applied to the fields of wood, plastics, coatings, papermaking, textiles, leather, medicine, construction, light industry and the like, and can also be used as a polymerization inhibitor, a water reducing agent, a glass fiber binder, a formaldehyde cleaning agent and the like. In recent years, melamine is regarded as the most cheap raw material for preparing visible-light-driven photocatalyst graphite-phase Carbon Nitride (CN) and further receives attention, but the prepared CN has extremely low specific surface area and poor photocatalytic performance, and the structure of the melamine is one of the reasons for the phenomenon. Chinese patent document CN105597803A discloses a mesoporous carbon nitride photocatalyst and a preparation method thereof, which is mainly characterized in that mesoporous carbon is used as a template to prepare mesoporous carbon nitride, and the mesoporous carbon nitride photocatalyst can be simply preparedThe template agent is easy to remove, the influence on the prepared mesoporous carbon nitride is small, and the mesoporous carbon nitride has a high specific surface area. The preparation steps are as follows: firstly, polyether polymer is taken as a template agent, beta-cyclodextrin is taken as a carbon source, and mesoporous carbon is obtained through low-temperature polymerization and high-temperature calcination; secondly, the prepared mesoporous carbon is used as a template, and after melamine is thermally polymerized at high temperature, the mesoporous carbon template is removed to prepare the mesoporous carbon nitride with high specific surface area. The method has simple process and low cost, and the prepared mesoporous carbon nitride photocatalyst has higher visible light catalytic activity. In the prior art, a carbon source is mainly modified to prepare mesoporous carbon, and then the mesoporous carbon is utilized to prepare mesoporous carbon nitride with high specific surface area, but the modification of melamine is rarely reported.
At present, common commercial melamine powder is mainly composed of large particles of several tens of micrometers, and is of a non-porous structure. Although melamine sponge which has been developed in recent years is of a porous structure, the melamine sponge is mainly macroporous and almost has no mesopores, and the unique properties of mesoporous materials are obvious. Therefore, the application of the mesoporous melamine in the fields of flame retardance, building, CN preparation and the like is urgently sought, and the research and development of the preparation technology of the mesoporous melamine are particularly urgent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of melamine with a high specific surface area and a multilevel structure, the method has simple process and low cost, and the prepared melamine with the multilevel structure contains a large number of mesopores, has high specific surface area, and is more than forty times of common commercial melamine powder.
The technical scheme of the invention is as follows:
a preparation method of melamine with a high specific surface area and a multilevel structure comprises the following steps:
(1) stirring and dispersing melamine powder in a mixed solution of alcohol and acid to obtain a dispersion liquid;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 10-80 ℃ for 1-24 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing with alcohol, and drying to obtain the high-specific-surface-area multi-stage-structure melamine.
Preferably according to the invention, the melamine powder in step (1) is a common commercial product; preferably, the melamine powder in step (1) is available from national pharmaceutical group chemical agents, ltd, cat # 30112528.
According to the invention, the alcohol in the steps (1) and (3) is one or more of absolute methanol, absolute ethanol, ethylene glycol, propylene glycol and glycerol; preferably, the alcohol is absolute ethyl alcohol.
According to the invention, the acid in the step (1) is one or more of concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid, concentrated formic acid or concentrated hypochlorous acid; preferably, the acid is one of concentrated hydrochloric acid, concentrated nitric acid and concentrated phosphoric acid; further preferably, the acid is concentrated hydrochloric acid.
More preferably, the mass concentration of the concentrated hydrochloric acid is 36 to 38%, the mass concentration of the concentrated nitric acid is 21 to 23%, the mass concentration of the concentrated phosphoric acid is 83 to 87%, the mass concentration of the concentrated formic acid is 87 to 89%, and the mass concentration of the concentrated hypochlorous acid is 10 to 13%.
According to the invention, the volume ratio of the acid to the alcohol in the step (1) is 1 (2-50); preferably, the volume ratio of the acid to the alcohol is 1: 10.
According to the invention, the concentration of the melamine powder in the dispersion liquid in the step (1) is preferably 0.01-0.20 g/mL, and the concentration of the melamine powder in the dispersion liquid is preferably 0.10 g/mL.
Preferably, according to the invention, the stirring temperature in step (2) is 25 ℃.
According to the invention, the stirring time in step (2) is preferably 2 h.
According to the invention, the drying in the step (3) is preferably performed at 50-100 ℃ for 5-24 h; preferably, the drying is carried out at 60 ℃ for 12 h.
Preferably, according to the invention, the drying in step (3) is carried out in a forced air drying oven.
The invention has the technical characteristics that:
firstly, in the process of preparing the high specific surface area multi-stage structure melamine, the volume ratio of the acid to the alcohol in the step (1) is 1 (2-50); preferably, the volume ratio of the acid to the alcohol is 1: 10. The invention unexpectedly discovers that the ratio of acid to alcohol is very important in the process of preparing the melamine with the high specific surface area and the multilevel structure, and when the ratio is too high, a large amount of water is introduced, so that the solubility of melamine salt is influenced, and the formation of the multilevel structure is not facilitated. Too low a ratio is also not conducive to the formation of a multilevel structure.
The invention makes up the defects of the prior art and successfully prepares the melamine with high specific surface area and a multilevel structure. The inventors have found unexpectedly in long-term studies that melamine forms melamine salts (the acid is a strong acid) or melamine/acid hydrogen bond complexes (the acid is a weak acid) with acids, and that the acid salts or hydrogen bond complexes can be sparingly soluble in alcohols. This dynamic equilibrium process of dissolution, precipitation, enables "cutting" of the melamine, thus forming a multilevel structure.
The invention has the following beneficial effects:
1. compared with common commercial melamine powder, the high-specific surface area multi-stage structure melamine prepared by the invention contains a large number of mesopores, has high specific surface area and pore volume, can be obtained only by room temperature treatment with common acid, and has the advantages of simple preparation process, simple required equipment, low energy consumption, low cost and easy realization of industrial production.
2. The filtrate produced in the process of preparing the melamine with the high specific surface area and the multi-stage structure can be recycled, so that the cost is reduced, the wastewater discharge is reduced, and the requirements of low price and environmental protection are met.
3. The melamine with the high specific surface area and the multilevel structure prepared by the method has great application value in the fields of flame retardance, preparation of melamine foam plastics, CN and the like due to the high specific surface area.
Drawings
FIG. 1 is an SEM photograph of a melamine sample;
in the figure, (a) is an SEM photograph of a common commercial melamine powder; (b) SEM photograph of the alcohol-modified melamine prepared for comparative example 1; (c) SEM photograph of the melamine prepared in example 1; (d) is a partial magnified SEM photograph of the melamine prepared in example 1;
FIG. 2 shows N of a melamine powder as a conventional commercial product and the melamine prepared in example 12Adsorption and desorption isotherm graphs and pore size distribution graphs (inset);
in the figure: MA refers to common commercial melamine powder, MAH refers to the melamine prepared in example 1;
FIG. 3 shows N of CN prepared in comparative example 2 and MCN prepared in Experimental example 12Adsorption and desorption isotherm graphs;
FIG. 4 is a graph showing pore size distributions of CN prepared in comparative example 2 and MCN prepared in Experimental example 1;
FIG. 5 is a graph showing the degradation profile of rhodamine B under visible light for CN prepared in comparative example 2 and MCN prepared in experimental example 1.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Melamine powder was purchased from national pharmaceutical group chemical Co., Ltd, cat # 30112528.
In the examples described below, SEM photographs were obtained by observation with a Hitachi SU8010 field emission scanning electron microscope; n is a radical of2The adsorption and desorption isothermal curve is measured by a Quadrasorb EVO type full-automatic specific surface area and pore size analyzer of Congta instruments, USA, the specific surface area is obtained by a BET method, and the pore size distribution curve is obtained by processing adsorption line branches by a BJH method.
Example 1
A preparation method of melamine with a high specific surface area and a multilevel structure comprises the following steps:
(1) mixing 20mL of absolute ethyl alcohol and 1.55mL of concentrated hydrochloric acid solution with the mass concentration of 36% to obtain a mixed solution, and stirring and dispersing 2g of melamine powder in the mixed solution to obtain a dispersion solution;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 25 ℃ for 2 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing the precipitate by absolute ethyl alcohol, and drying the precipitate in a forced air drying oven at the temperature of 60 ℃ for 12 hours to obtain the high-specific-surface-area multi-stage structure melamine.
Example 2
A preparation method of melamine with a high specific surface area and a multilevel structure comprises the following steps:
(1) mixing 20mL of glycerol and 0.87mL of concentrated phosphoric acid solution with the mass concentration of 85% to obtain a mixed solution, and stirring and dispersing 2g of melamine powder in the mixed solution to obtain a dispersion liquid;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 70 ℃ for 5 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing the precipitate by absolute ethyl alcohol, and drying the precipitate for 10 hours in a forced air drying oven at 70 ℃ to obtain the high-specific-surface-area multi-stage structure melamine.
Example 3
A preparation method of melamine with a high specific surface area and a multilevel structure comprises the following steps:
(1) mixing 20mL of ethylene glycol and 10mL of nitric acid solution (3.2mL of concentrated nitric acid with the mass concentration of 69% is added into 6.8mL of water) to obtain a mixed solution, and stirring and dispersing 2g of melamine powder in the mixed solution to obtain a dispersion liquid;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 30 ℃ for 17 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing the precipitate by absolute ethyl alcohol, and drying the precipitate for 6 hours in a forced air drying oven at the temperature of 90 ℃ to obtain the high-specific-surface-area multi-stage structure melamine.
Comparative example 1
A preparation method of alcohol-modified melamine comprises the following steps:
(1) 2g of melamine powder is stirred and dispersed in 20mL of absolute ethyl alcohol to obtain dispersion liquid;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 25 ℃ for 2 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing the precipitate by absolute ethyl alcohol, and drying the precipitate in a forced air drying oven at the temperature of 60 ℃ for 12 hours to obtain the alcohol-modified melamine.
The morphology of the common commercial melamine powder is shown in fig. 1(a), and it can be seen that the common commercial melamine powder mainly consists of large particles with the particle size of tens of micrometers; the morphology of the melamine alcohol prepared in comparative example 1 is shown in fig. 1(b), and it can be seen from the figure that the melamine alcohol prepared in comparative example 1 has a similar morphology to that of the common commercial melamine powder, i.e. the ethanol does not cause the morphology of the common commercial melamine powder to change. The morphology of the high specific surface area hierarchical structure melamine prepared in example 1 is shown in fig. 1(c), a partial enlarged view is shown in fig. 1(d), and it can be seen from fig. 1(a) and 1(c) that the large particles of the common commercial melamine powder are transformed into the hierarchical structure composed of nanorods (or ribbons) in which the rods (or ribbons) are several micrometers long and have an average diameter of several tens to several hundreds of nanometers. The morphological difference between the common commercial melamine powder and the high specific surface area multi-stage structure melamine prepared in example 1 strongly explains the "cutting" effect of the acid.
N of common commercial melamine powder and high specific surface area multi-stage structure melamine prepared in example 12The adsorption and desorption isotherms and pore size distribution curves are shown in FIG. 2, N of common commercial melamine powder2The adsorption and desorption isotherm curve has no hysteresis loop and the pore size distribution curve has no peak, indicating a nonporous structure, and the specific surface area and the pore volume of the nonporous structure are respectively 0.28m2G and 3.9X 10–5cm3(ii) in terms of/g. N of the high specific surface area multi-stage structure melamine prepared in example 12The adsorption and desorption isotherm curve is IV type, and has an H3 type hysteresis loop, which indicates the existence of gap type mesopores, and the pore size distribution curve indicates that the pore size of the mesopores is mainly 2-8 nm, which is consistent with the SEM result in FIG. 1 (c). The specific surface area and the pore volume of the high specific surface area multi-stage structure melamine prepared in example 1 are respectively 12.46m2G and 1.8X 10–2cm3The/g is increased by about 44.5 times and 460 times compared with common commercial melamine powder.
Experimental example 1
Putting the melamine with the high specific surface area and the multi-stage structure prepared in the example 1 into a 20mL crucible, placing the crucible in a muffle furnace, setting the heating rate to be 5 ℃/min, heating to 550 ℃, preserving the heat for 4h, naturally cooling to room temperature, grinding the product into powder, and obtaining graphite-phase carbon nitride, which is marked as MCN.
Comparative example 2
Adding 2g of common commercial melamine powder into a 20mL crucible, placing the crucible in a muffle furnace, setting the heating rate to be 5 ℃/min, heating to 550 ℃, preserving heat for 4h, naturally cooling to room temperature, grinding the product into powder, and obtaining graphite-phase carbon nitride, which is recorded as CN.
The preparation of graphite phase carbon nitride is an application of melamine in the field of photocatalysis. MCN prepared in Experimental example 1 and N of CN prepared in comparative example 22The adsorption and desorption isotherms are shown in FIG. 3, the pore size distribution is shown in FIG. 4, and the results show that CN and MCN both have IV-type isotherms and H3 hysteresis loops, i.e., mesoporous structures, and the specific surface area and pore volume of CN are respectively 6.67m2G and 3.35X 10–2cm3G, and MCN are each 13.01m2G and 6.23X 10–2cm3The concentration/g is obviously increased compared with CN, particularly, the pore size distribution curve of MCN shows the generation of new mesopores, and the pore size range is 2-6 nm.
The MCN prepared in the experimental example 1 and the CN prepared in the comparative example 2 are applied to degradation of rhodamine B (10mg/L), and the degradation rate of the rhodamine B under visible light is shown in FIG. 5. As can be seen from FIG. 5, rhodamine B itself is hardly degraded, and the degradation rate of MCN on rhodamine B is significantly greater than that of CN, indicating that carbon nitride prepared by using the melamine with the high specific surface area and the multilevel structure prepared in example 1 as the raw material has higher photocatalytic activity than carbon nitride prepared by using common commercial melamine powder as the raw material.
It is clear that the above examples and experimental examples of the invention are only simple applications of melamine in numerous fields of application, are intended to illustrate the broad scope of the invention clearly and are not intended to limit the field of application and the embodiments of the invention. Other variations may be made in specific circumstances for specific applications in various fields. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of melamine with a high specific surface area and a multilevel structure comprises the following steps:
(1) stirring and dispersing melamine powder in a mixed solution of alcohol and acid to obtain a dispersion liquid;
the volume ratio of the acid to the alcohol is 1 (2-50); the concentration of the melamine powder in the dispersion liquid is 0.01-0.20 g/mL;
(2) stirring the dispersion liquid in the step (1) at a stirring temperature of 10-80 ℃ for 1-24 hours;
(3) and (3) filtering the dispersion liquid stirred in the step (2), collecting the precipitate, washing with alcohol, and drying to obtain the high-specific-surface-area multi-stage-structure melamine.
2. The method according to claim 1, wherein the alcohol in steps (1) and (3) is one or more of absolute methanol, absolute ethanol, ethylene glycol, propylene glycol and glycerol.
3. The method according to claim 1, wherein the acid in step (1) is one or more of concentrated hydrochloric acid, concentrated nitric acid, concentrated phosphoric acid, concentrated formic acid, and concentrated hypochlorous acid.
4. The method according to claim 3, wherein the mass concentration of the concentrated hydrochloric acid is 36 to 38%, the mass concentration of the concentrated nitric acid is 21 to 23%, the mass concentration of the concentrated phosphoric acid is 83 to 87%, the mass concentration of the concentrated formic acid is 87 to 89%, and the mass concentration of the concentrated hypochlorous acid is 10 to 13%.
5. The method of claim 1, wherein the stirring temperature in step (2) is 25 ℃.
6. The method according to claim 1, wherein the stirring time in the step (2) is 2 hours.
7. The method according to claim 1, wherein the drying in the step (3) is performed at 50 to 100 ℃ for 5 to 24 hours.
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| JP5582527B2 (en) * | 2010-03-23 | 2014-09-03 | 独立行政法人産業技術総合研究所 | Method for producing graphitic carbon nitride |
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