CN112978706B - Method for preparing high-strength carbon pellets by taking polyvinylidene chloride as raw material - Google Patents
Method for preparing high-strength carbon pellets by taking polyvinylidene chloride as raw material Download PDFInfo
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- CN112978706B CN112978706B CN201911283101.3A CN201911283101A CN112978706B CN 112978706 B CN112978706 B CN 112978706B CN 201911283101 A CN201911283101 A CN 201911283101A CN 112978706 B CN112978706 B CN 112978706B
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- polyvinylidene chloride
- porous carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention discloses a method for preparing nitrogen-containing porous carbon spheres by using polyvinylidene chloride and melamine as precursors. Specifically, melamine and polyvinylidene chloride are uniformly mixed to prepare a spherical material. Roasting the obtained pellets at high temperature to obtain the nitrogen-containing porous carbon pellets in one step. The method is simple to operate, and avoids the later activation process of the traditional porous carbon material. The high-strength porous carbon spheres obtained by the invention have wide application prospects in the fields of catalysis and adsorption.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method of a polyvinylidene chloride emulsion doped melamine porous carbon material.
Technical Field
The active carbon as an excellent adsorption separation material has the characteristics of large specific surface area, developed pore structure, stable chemical property and acid and alkali resistance, the excellent adsorption performance of the active carbon mainly depends on the special pore structure, and the active carbon has high specific surface area and adsorption capacity due to the existence of a large number of micropores and mesopore structures. The preparation of raw materials and conditions make the pore structure adjustable. The spherical porous carbon material has the excellent performances of regular shape, smooth surface, uniform filling density, small resistance and the like, and is widely applied to the fields of adsorption, catalysis, medical treatment and the like. When spherical activated carbon is prepared from pitch and ion exchange resin, it is generally pyrolyzed and then physically or chemically activated. During activation, the molecules of the activating substance react with the carbon to etch away a portion of the carbon, thereby forming pores and increasing the specific surface area, but this may reduce the strength of the spherical carbon material.
Polyvinylidene chloride can form a microporous carbon material with a high specific surface area in the pyrolysis process, but the polyvinylidene chloride particles sold in the market are small, and a spherical carbon material with a certain particle size can be obtained only by carbonizing after forming. In the invention, the spherical polyvinylidene chloride-melamine composite particles are prepared by an alginic acid-assisted sol-gel method. The addition of melamine can introduce nitrogen species in the carbonization process on one hand, and on the other hand, after the melamine is completely pyrolyzed, the space occupied by the melamine forms a macroporous structure, which is favorable for the diffusion process of adsorption-desorption of adsorbed molecules in particles.
Disclosure of Invention
The invention aims to provide a method for preparing nitrogen-containing porous carbon pellets by using polyvinylidene chloride and melamine as precursors. Specifically, melamine and polyvinylidene chloride are uniformly mixed to prepare a spherical material. Roasting the obtained pellets at high temperature to obtain the nitrogen-containing porous carbon pellets in one step. The method is simple to operate and has good material controllability.
The purpose of the invention can be realized by the following technical scheme.
A method for preparing nitrogen-containing porous carbon pellets by using polyvinylidene chloride precursor and melamine as raw materials comprises the following specific steps:
(1) Uniformly mixing a polyvinylidene chloride precursor, melamine, sodium alginate and water according to different mass ratios;
(2) Dropwise adding the solution prepared in the step (1) into a coagulating bath;
(3) And (3) roasting the pellets obtained in the step (2) in an inert atmosphere to obtain the spherical porous carbon material.
The polyvinylidene chloride precursor in the step (1) is one or two of polyvinylidene chloride powder or emulsion, and the average grain diameter is 0.01-500 mu m.
The melamine in the step (1) has an average particle diameter of 0.01 to 500. Mu.m.
The mixed solution in the step (1) is 0.2 to 7 mass%, preferably 0.2 to 2 mass% of sodium alginate.
The mixed solution in the step (1) has a mass fraction of the polyvinylidene chloride precursor of 20 to 50%, preferably 25 to 40%.
The mass fraction of melamine in the mixed solution in the step (1) is 1-40%, preferably 5-20%.
The coagulating bath in the mixed solution in the step (2) is one or more of aqueous solutions of salts of Ca, sr, ba, al, mn, fe, co, ni, cu and Zn.
The total concentration of the cations in the coagulating bath in the step (2) is 0.1-2mol/L, and the volume ratio of the coagulating bath solution to the suspension is 1.5-100.
The inert gas in the step (3) is N 2 One or more of Ar and He gas.
The material roasting heating rate in the step (3) is 0.1-10 ℃/min.
The roasting temperature in the step (3) is 600-1000 ℃, and the heat preservation time is 0.5-12h.
The method is simple to operate, and avoids the later activation process of the traditional porous carbon material. The high-strength porous carbon ball obtained by the invention has wide application prospect in the fields of catalysis and adsorption.
Detailed Description
The following examples are presented to further illustrate the present invention.
Example 1
Mixing 20.00g of melamine (with average particle size of 20-100 mu m), 40.00g of water, 30.00g of polyvinylidene chloride emulsion (with average particle size of 0.1-1 mu m) with the mass content of 55% and 24.96g of sodium alginate solution with weight percent of 5 percent, stirring for 30min, and dropwise adding the obtained uniform suspension to 500ml of 0.5mol/L CaCl 2 Stirring for 5min after the dropwise addition, and placing the sample in CaCl 2 The solution was soaked overnight and the sample tray was placed in a fume hood for drying.
Placing the obtained sample in a tube furnace, heating to 800 ℃ at a speed of 2 ℃/min in Ar protective atmosphere, preserving heat for 6h, cooling the sample along with the furnace, wherein the N mass content of the product is 7%, and the specific surface area is 260m 2 Per g, pore volume of 0.89cm 3 1bar of CO 2 The adsorption amount was 3.5mmol/g.
Example 2
Mixing 8.75g melamine (average particle size 20-100 μm), 20.01g water, 16.25g polyvinylidene chloride powder (average particle size 20-100 μm), 12.45g 0.9wt% sodium alginate solution, stirring for 30min, and dropwise adding the obtained uniform suspension to 200ml 1mol/L Ca (NO) 3 ) 2 Adding into the solution, stirring for 5min after dropwise adding, and placing the sample in SrCl 2 The solution was soaked overnight and the sample tray was placed in a fume hood for drying.
The resulting sample was placed in a tube furnace, N 2 Raising the temperature to 600 ℃ at the speed of 2 ℃/min in a protective atmosphere, preserving the heat for 5 hours, cooling the sample along with the furnace, wherein the N mass content of the product is 4.5 percent, and the specific surface area is 300m 2 Per g, pore volume of 0.70cm 3 1bar of CO 2 The adsorption amount was 4.0mmol/g.
Example 3
Mixing 5.00g of melamine (average particle size of 20-100 μm), 20.00g of water, 20.00g of polyvinylidene chloride (average particle size of 2-20 μm) emulsion with the mass content of 40% and 12.45 wt% sodium alginate solution, stirring for 30min, and dropwise adding the obtained uniform suspension to 400ml of 0.3mol/L Mn (NO) (NO: 3) 3 ) 2 Adding into the solution, stirring for 5min, and placing the sample in BaCl 2 The solution was soaked overnight and the sample tray was placed in a fume hood for drying.
Placing the obtained sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min in He protective atmosphere, preserving heat for 6h, cooling the sample along with the furnace, wherein the N mass content of the product is 2.5%, and the specific surface area is 370m 2 Per g, pore volume of 0.87cm 3 1bar of CO 2 The adsorption amount was 2.5mmol/g.
Example 4
Mixing 7.05g melamine (average particle size of 20-100 μm), 20.00g water, 10.65g polyvinylidene chloride powder (average particle size of 100-200 μm), 12.49.1 wt% sodium alginate solution, stirring for 30min, and dropwise adding the obtained uniform suspension to 100ml 2mol/L BaCl 2 、CaCl 2 (the molar ratio of the two salts is 1) 2 The solution was soaked overnight and the sample tray was placed in a fume hood for drying.
The resulting sample was placed in a tube furnace, ar: n is a radical of 2 In a protective atmosphere of =1 (volume ratio) 3, raising the temperature to 900 ℃ at a speed of 1 ℃/min, preserving the heat for 6h, cooling the sample along with the furnace, wherein the N mass content of the product is 6.5%, and the specific surface area is 390m 2 Per g, pore volume of 0.65cm 3 1bar of CO 2 The adsorption amount was 3.0mmol/g. .
Example 5
Mixing 7.50g of melamine (with the average particle size of 20-100 mu m), 40.00g of water, 42.50g of polyvinylidene chloride emulsion (with the average particle size of 20-100 mu m) with the mass content of 55 percent and 24.89 wt percent sodium alginate solution, stirring for 30min, and dropwise adding the obtained uniform suspension to 1000ml of 0.2mol/L CaCl 2 Stirring for 5min after the dropwise addition, and placing the sample in CaCl 2 The solution is soaked in the water for one night,the sample-containing trays were placed in a fume hood for drying.
The resulting sample was placed in a tube furnace, ar: he =2:1 (volume ratio) in protective atmosphere, heating to 700 ℃ at a temperature of 10 ℃/min, preserving heat for 6h, cooling along with the furnace, wherein the N mass content of the product is 5.0 percent, and the specific surface area is 500m 2 Per g, pore volume 0.54cm 3 1bar of CO 2 The adsorption amount was 2.0mmol/g.
Claims (8)
1. A method for preparing nitrogen-containing porous carbon pellets by using polyvinylidene chloride precursor and melamine as raw materials is characterized by comprising the following steps:
(1) Uniformly mixing a polyvinylidene chloride precursor, melamine, sodium alginate and water according to different mass ratios; the mass fraction of the sodium alginate in the mixed solution is 0.2 to 7 percent; the mass fraction of the polyvinylidene chloride precursor in the mixed solution is 20-50%, and the mass fraction of the melamine in the mixed solution is 1-40%;
(2) Dropwise adding the solution prepared in the step (1) into a coagulating bath;
(3) Roasting the pellets obtained in the step (2) in an inert atmosphere to obtain a spherical porous carbon material; the high-temperature roasting temperature is 600-1000 ℃, and the heat preservation time is 0.5-12h.
2. The method for preparing nitrogen-containing porous carbon pellets according to claim 1, characterized in that: the polyvinylidene chloride precursor is one or two of polyvinylidene chloride powder or polyvinylidene chloride emulsion, and the average particle size of the polyvinylidene chloride is 0.01-500 μm.
3. The method for preparing nitrogen-containing porous carbon pellets according to claim 1, characterized in that: the melamine has an average particle size of 0.01 to 500 μm.
4. The method for preparing nitrogen-containing porous carbon pellets according to claim 1, characterized in that:
the mass fraction of the sodium alginate in the mixed liquid in the step (1) is 0.2-2%;
the mass fraction of the polyvinylidene chloride precursor in the mixed solution in the step (1) is 25-40%;
the mass fraction of melamine in the mixed solution obtained in the step (1) is 5-20%.
5. The method for producing nitrogen-containing porous carbon pellets according to claim 1, wherein the coagulation bath is one or more of aqueous solutions of salts of Ca, sr, ba, al, mn, fe, co, ni, cu and Zn; the total concentration of the cations in the coagulating bath is 0.1-2 mol/L.
6. The process for producing nitrogen-containing porous carbon beads according to claim 1, 4 or 5, wherein the volume ratio of the coagulation bath solution to the suspension is 1.5 to 100.
7. The process for producing nitrogen-containing porous carbon beads according to claim 1, wherein the inert gas is N 2 One or more of Ar and He gas.
8. The method for preparing nitrogen-containing porous carbon pellets according to claim 1, characterized in that: the heating rate of the material from room temperature to roasting temperature is 0.1-10 ℃/min.
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