CN111013537A - Preparation of sulfonic group regular mesoporous carbon and application of sulfonic group regular mesoporous carbon in ammonia adsorption - Google Patents
Preparation of sulfonic group regular mesoporous carbon and application of sulfonic group regular mesoporous carbon in ammonia adsorption Download PDFInfo
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Abstract
The invention belongs to the field of preparation of inorganic materials, and particularly relates to sulfonic group regular mesoporous carbon, a preparation method thereof and application thereof in ammonia gas adsorption. The invention adopts a phenol organic compound and an aldehyde organic compound as raw materials, a block copolymer as a template agent is synthesized in one step to obtain a regular mesoporous polymer, the regular mesoporous polymer is used as a precursor, and a sulfonic group regular mesoporous carbon is synthesized through carbonization and sulfonation, and the sulfonic group regular mesoporous carbon has a body-centered cubic mesostructure and a specific surface area of 700-1000 m2The volume is 20-40 meshes. The nitrogen-doped ordered mesoporous carbon material provided by the invention has the advantages of strong aperture adjustability, high thermal stability, simple preparation process, easiness in realization of industrial production and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of material science, and particularly relates to sulfonic group ordered mesoporous carbon and a preparation method and application thereof.
Background
Ammonia gas is a common colorless alkaline gas with irritant odor, is active in chemical property and is easily oxidized to form NO3 -Or NOx -Not only can damage the ecological structure and pollute the environment, but also can damage the skin tissues and the respiratory system of human beings, thereby seriously threatening the health of human beings. Therefore, the problem of ammonia removal has become an increasingly important issue in countries around the world. Common ammonia gas treatment methods at home and abroad mainly comprise an adsorption method, an absorption method, a biological method, a plasma method and the like. The adsorption method can effectively remove low-concentration pollutants, has high removal efficiency and simple equipment, and is easy to recover and gradually becomes a mainstream method for removing industrial ammonia gas.
The traditional ammonia gas adsorbent comprises porous materials such as activated carbon, zeolite, alumina and mixtures thereof. The active carbon and the zeolite are adsorbents with high industrial value from the aspects of process preparation and economic calculation, but the adsorption quantity of the pure active carbon and the zeolite is not high, the active carbon and the zeolite need to be acidified and modified, the investment and the operation cost are high, and the use cost is increased. The alumina and the mixture thereof are porous, have large specific surface area, have more hydroxyl functional groups on the surface and have good adsorption performance, but the use limitation is that the preparation process is complex, the price is higher, the water absorption is strong, and the ammonia adsorption material has harmful effect on human bodies, so that the ammonia adsorption material is difficult to become the mainstream.
The regular mesoporous polymer has the structural characteristics of high specific surface area, adjustable pore diameter, unique organic framework, regular pore channel structure and the like, and has wide application prospect in high and new fields of heterogeneous catalysis, gas adsorption, biomedicine, nano devices and the like. At present, the regular mesoporous polymer mainly takes phenolic resin and derivatives thereof as main materials, has low preparation cost, controllable surface wettability and excellent acid and alkali resistance, draws people's extensive attention, and is successfully applied to a plurality of research fields. Aiming at the problems, the invention designs and develops a solvent-free technology to realize the preparation of the highly regular mesoporous phenolic resin material, and prepares the sulfonic group regular mesoporous carbon by taking the mesoporous phenolic resin material as a precursor through carbonization and sulfonation, and the sulfonic group regular mesoporous carbon is applied to the field of ammonia gas adsorption, and simultaneously shows excellent performance in selective adsorption of low-concentration ammonia gas in raw material gas by optimizing material structure parameters. The method has important practical significance for realizing the efficient preparation of the regular mesoporous phenolic resin and the selective removal of ammonia.
Disclosure of Invention
Aiming at the technical defects that the current synthesis cost is high, the preparation process is complicated, the mass use of a solvent and a strong acid or strong base catalyst is not beneficial to industrial production and the like, the invention synthesizes the sulfonic group regular mesoporous carbon by simple, convenient and rapid solvent-free synthesis and applies the sulfonic group regular mesoporous carbon to NH3Selective adsorption of (3).
In order to solve the technical problems, the invention adopts the following specific technical scheme:
a preparation method of sulfonic group regular mesoporous carbon adopts a phenol organic compound and an aldehyde organic compound as raw materials, a block copolymer as a template agent to synthesize a regular mesoporous polymer in one step, and the regular mesoporous polymer is used as a precursor to synthesize the sulfonic group regular mesoporous carbon through carbonization and sulfonation. Wherein the molar ratio of the phenolic hydroxyl group in the phenolic organic compound to the carbonyl group in the aldehyde organic compound is 1: 0.5-1: 5.
Further, the phenolic organic compound is one or more of m-aminophenol, resorcinol and phloroglucinol.
Further, the aldehyde organic compound is one or more of terephthalaldehyde and benzaldehyde.
Further, the block copolymer templating agent is F127 or P123.
The preparation method of the sulfonic group regular mesoporous carbon specifically comprises the following steps:
(1) weighing a certain amount of block copolymer template agent, phenolic organic compound and aldehyde organic compound, mechanically and uniformly mixing, and then putting into a ceramic burning boat;
(2) transferring the sample obtained in the step (1) to a tubular furnace, and carbonizing the sample in a nitrogen atmosphere;
(3) mixing the sample obtained in the step (2) with KOH, transferring the mixture into a tubular furnace, and roasting the mixture in a nitrogen atmosphere;
(4) neutralizing the sample obtained in the step (3) with an acid solution, then washing with water to be neutral, and drying to obtain a nitrogen-doped ordered mesoporous carbon material OMC;
(5) and (3) weighing 1g of the sample obtained in the step (4), placing the sample in a reaction kettle with a polytetrafluoroethylene substrate, adding concentrated sulfuric acid, sulfonating for 12 hours at a certain reaction temperature, washing the sample to be neutral by using deionized water, and finally drying the sample in vacuum at 100 ℃ to obtain the sulfonic group regular mesoporous carbon S-OMC.
Further, the mechanical blending in the step (1) is to grind and mix the mixture in a mortar for 10-20 min.
Further, carbonizing at 700-900 ℃ for 1-3h in the step (2).
Further, the mass ratio of the sample to KOH in the step (3) is 1:1, and the roasting is carried out at 700-900 ℃ for 2 h.
Further, the acid solution in the step (4) is 1M HCl, and the drying is performed for 8-12 hours at the temperature of 60 ℃.
Further, the volume of the concentrated sulfuric acid in the step (5) is 10-30 ml, and the temperature of the sulfonation reaction is 90-140 ℃.
The sulfonic group regular mesoporous carbon can be used for ammonia adsorption, the adsorption reaction temperature is 0-40 ℃, and the filling amount of the sulfonic group regular mesoporous carbon is 30-100 mg; the adsorption reaction pressure is 0 bar-2 bar.
The technical scheme of the invention has the following advantages:
1. the solvent-free prepared regular mesoporous phenolic resin provided by the invention has strong aperture adjustability, high material thermal stability, simple and green preparation process, easy realization of industrial production and wide application prospect;
2. the nitrogen-doped ordered mesoporous carbon material provided by the invention has a bodyThe specific surface area of the mesoscopic structure of the core cube is as high as 700-1000 m2The catalyst has good adsorption activity in ammonia gas adsorption performance reaction tests;
3. the regular mesoporous carbon provided by the invention can greatly change the surface property of the material after sulfonation, enhance the hydrophilicity of the material, improve the surface acidity of the material, and facilitate the exposure of acid sites due to large specific surface area, thereby enhancing the ammonia gas adsorption capacity of the material.
Drawings
FIG. 1 shows the ammonia adsorbent F at 0 ℃ for NH3、N2And H2Adsorption graph of (a);
FIG. 2 is a scanning electron micrograph of the ammonia adsorbent A.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
Example 1
Weighing 2.1g F127 template, 0.39g m-aminophenol and 0.69g terephthalaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, carbonizing at 700 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tubular furnace, carbonizing at 700 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutrality, drying to obtain ordered mesoporous carbon, weighing 1g of the ordered mesoporous carbon, placing into a reaction kettle with a polytetrafluoroethylene substrate, adding 12ml of concentrated sulfuric acid, sulfonating at 120 ℃ for 12h, washing with deionized water to neutrality, and finally drying at 100 ℃ in vacuum to obtain the sulfonic group regular mesoporous carbon S-OMC. The mark is an ammonia adsorbent A, and fig. 2 is a transmission electron microscope picture of the ammonia adsorbent A, and the existence of the ordered pore channels can promote the diffusion and mass transfer of guest molecules with different sizes, so that the ammonia adsorption can be efficiently promoted.
Example 2
Weighing 2.2g F127 template, 0.44g resorcinol and 0.61g benzaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tube furnace, carbonizing at 800 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tube furnace, carbonizing at 800 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutral and drying to obtain ordered mesoporous carbon, weighing 1g and placing in a reaction kettle with a polytetrafluoroethylene substrate, adding 15ml concentrated sulfuric acid, sulfonating at 120 ℃ reaction temperature for 12h, washing with deionized water to neutral, and finally vacuum drying at 100 ℃ to obtain the sulfonic group regular mesoporous carbon S-OMC. And is marked as ammonia adsorbent B.
Example 3
Weighing 2.3g P123 template, 0.45g m-aminophenol and 0.67g terephthalaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, carbonizing at 800 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tubular furnace, carbonizing at 800 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutrality, drying to obtain ordered mesoporous carbon, weighing 1g of the ordered mesoporous carbon, placing into a reaction kettle with a polytetrafluoroethylene substrate, adding 12ml of concentrated sulfuric acid, sulfonating at 140 ℃ for 12h, washing with deionized water to neutrality, and finally drying at 100 ℃ in vacuum to obtain the sulfonic group regular mesoporous carbon S-OMC. And is marked as ammonia adsorbent C.
Example 4
Weighing 2.1g F127 template, 0.55g phloroglucinol and 0.61g terephthalaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, carbonizing at 900 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tubular furnace, carbonizing at 800 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutrality, drying to obtain ordered mesoporous carbon, weighing 1g of the ordered mesoporous carbon, placing into a reaction kettle with a polytetrafluoroethylene substrate, adding 15ml of concentrated sulfuric acid, sulfonating at 140 ℃ for 12h, washing with deionized water to neutrality, and finally drying at 100 ℃ in vacuum to obtain the sulfonic group regular mesoporous carbon S-OMC. And is marked as ammonia adsorbent D.
Example 5
Weighing 2.5g P123 template, 0.55g m-aminophenol and 0.61g terephthalaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, carbonizing at 900 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tubular furnace, carbonizing at 800 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutrality, drying to obtain ordered mesoporous carbon, weighing 1g of the ordered mesoporous carbon, placing in a reaction kettle with a polytetrafluoroethylene substrate, adding 15ml of concentrated sulfuric acid, sulfonating at 140 ℃ for 12h, washing with deionized water to neutrality, and finally drying at 100 ℃ in vacuum to obtain the sulfonic group regular mesoporous carbon S-OMC. And is marked as ammonia adsorbent E.
Example 6
Weighing 2.5g F127 template, 0.51g m-aminophenol and 0.53g terephthalaldehyde in a mortar, grinding uniformly and loading into a ceramic burning boat, transferring the ceramic burning boat into a tubular furnace, carbonizing at 800 ℃ for 60min in nitrogen atmosphere, mixing the carbonized sample with KOH with equal mass ratio, transferring into the tubular furnace, carbonizing at 800 ℃ for 2h in nitrogen atmosphere, neutralizing with hydrochloric acid, washing with water to neutrality, drying to obtain ordered mesoporous carbon, weighing 1g of the ordered mesoporous carbon, placing into a reaction kettle with a polytetrafluoroethylene substrate, adding 12ml of concentrated sulfuric acid, sulfonating at 140 ℃ for 12h, washing with deionized water to neutrality, and finally drying at 100 ℃ in vacuum to obtain the sulfonic group regular mesoporous carbon S-OMC. Denoted as ammonia adsorbent F.
Comparative example 1
(1) Adding 9 parts by weight of polyethylene glycol, 6 parts by weight of ethyl orthosilicate, 4 parts by weight of hexadecyl trimethyl ammonium bromide and 2.4 parts by weight of bromohexadecyl pyridine into 20 parts by weight of nitric acid solution, heating, keeping the temperature and stirring, adding NH4OH 9 parts, washing a product with ethanol, and drying to obtain powder I;
(2) mixing 6 parts by weight of ammonium polyvinyl alcohol phosphate, 7 parts by weight of diammonium hydrogen phosphate, 4 parts by weight of sodium thiosulfate and 8 parts by weight of anhydrous sodium carbonate, smelting, quenching the molten material in water, and crushing the generated blocks to obtain powder II;
(3) mixing the powder I obtained in the step 1 and the powder II obtained in the step 2, adding 10 parts by weight of lanthanum nitrate, and cooling at room temperature after calcining in a muffle furnace to obtain powder III;
(4) and grinding the powder III to the average particle size of 6 microns to obtain the powder III. Denoted as ammonia adsorbent F.
Comparative example 2
The embodiment provides a preparation method of a regular mesoporous phenolic resin with tetrahydrofuran and water as solvents and F127 as a block template agent, which comprises the following steps:
(1) 1.5g F127 was dissolved by stirring in 8 g of tetrahydrofuran and 6.5g of water, followed by 1.25g of phloroglucinol and stirring at room temperature for half an hour to effect self-assembly between the templating agent and phloroglucinol.
(2) Adding 2.0g of formaldehyde solution into the system, stirring at room temperature for 1h, and volatilizing the solvent at room temperature after uncovering for about 24 h.
(3) And thermally curing the solid in the reaction system at 120 ℃ for 24 hours to obtain a mesoporous phenolic resin primary product.
(4) And dispersing the primary product in a mixed solution of 50ml of ethanol and 7ml of concentrated hydrochloric acid, and refluxing at 90 ℃ for 24 hours to obtain a mesoporous phenolic resin material with open pore channels, wherein the mesoporous phenolic resin material is marked as an ammonia gas adsorbent G.
And (3) characterization and analysis:
N2physical adsorption: the specific surface area and pore size of the sample were measured at a liquid nitrogen temperature (-196 ℃) using an ASAP2020 analyzer from Micrometric corporation, USA, the sample was first pretreated under vacuum at 200 ℃ and then degassed at a pressure of less than 10-5torr for 3 hours, the specific surface area of the sample was calculated by the BET (Brunauer-Emmett-Teller) method, and the pore size distribution curve was determined by the BJH (Barrett-Joyner-Halenda) method.
TABLE 1 physicochemical Properties of Ammonia adsorbents prepared in inventive examples 4 to 6 and comparative examples 1 to 2
As can be seen from the comparison of the physical and chemical properties of the ammonia adsorbents prepared in examples 4 to 6 and comparative examples 1 to 2, the ratio of the three samples in examples 4 to 6 is shown in the tableThe surface is 700-1000 m2In the range of/g, the average pore diameter is about 3.5nm, the specific surface area of the ammonia adsorbent F is the largest, and the micropore content is the highest.
The ammonia adsorbents prepared in examples 1 to 6 and comparative examples 1 to 2 were numbered as A to H in this order, and were evaluated for ammonia adsorption performance by using an ammonia absorption tank and a buffer tank manufactured by Feiyu Petroleum science and technology development Co., Ltd, Nanjing, and a pressure sensor manufactured by Nanjing Tian from electric Co., Ltd.
The specific experiment for evaluating the ammonia gas adsorption performance is as follows:
the adsorbent was dried prior to testing, i.e., dried overnight at 150 ℃ in a vacuum oven to remove moisture and gases from the sample.
Firstly, 0.1g of adsorbent (20-40 meshes) is filled into an absorption tank, the absorption tank is screwed, then the buffer tank and the absorption tank are transferred into a constant-temperature (20 ℃) water bath kettle, and the temperature in the absorption tank is ensured to be consistent with the system temperature by observing the pressure change of a pressure digital display meter of the buffer tank and the absorption tank. Then, the air in the buffer tank and the adsorption tank is exhausted by a vacuum pump, helium is filled into the buffer tank and the adsorption tank to enable the pressure in the kettle to reach a certain pressure (1.5 bar) for leak detection, and the free volume in the adsorption tank is calculated. And finally, discharging helium gas in the buffer tank and the absorption tank, filling 2.5 bar of ammonia gas into the buffer tank, injecting 0.1 bar of ammonia gas into the absorption tank every two hours through a needle valve between the buffer tank and the absorption tank, and recording pressure data after the pressure is stable.
The adsorbents prepared in the examples and comparative examples were applied to ammonia gas adsorption reaction, and the ammonia gas adsorption performance was evaluated by the following criteria:
further, in the ammonia gas adsorption performance evaluation index, the adsorption experiment temperature is 0 ℃.
Furthermore, in the ammonia gas adsorption performance evaluation index,
、
、
representing buffer tank volume, absorber tank volume, and sample volume, respectively.
Furthermore, in the ammonia gas adsorption performance evaluation index,
representing the initial buffer tank ammonia gas density at the test temperature T.
Furthermore, in the ammonia gas adsorption performance evaluation index,
representative of a test temperature of T and a buffer tank pressure of
The gas density in the buffer tank.
Furthermore, in the ammonia gas adsorption performance evaluation index,
representative of a test temperature of T and an absorption tank pressure of
The density of the ammonia gas.
TABLE 2 evaluation index of ammonia gas adsorption performance of mesoporous carbon materials prepared in the examples and comparative examples of the present invention
As can be seen from Table 2, when the reaction system is 0 ℃ and the pressure of the absorption tank is 1bar, the sulfonic acid group regular mesoporous carbon (samples A-F) of the invention can reach higher ammonia gas adsorption capacity,the ammonia gas adsorption amount of the sample F is up to 9.2mmol/g, and meanwhile, the ammonia gas adsorption amounts of the samples A, C-F are respectively up to 6.6 mmol/g, 7.8mmol/g, 6.8mmol/g, 7.7 mmol/g and 8.9 mmol/g, so that the sample F has higher ammonia gas adsorption performance. The ammonia gas adsorption capacity of the comparative sample G, H is only 1.2mmol/g and 0.8 mmol/g, and the adsorption capacity is poor. Then respectively carrying out NH on the ammonia adsorbent F at the temperature of 0 DEG C3、N2And H2The adsorption curve of FIG. 1 is obtained by static adsorption test, and the selectivity of NH 3/N2 and NH 3/H2 is calculated to be as high as 82.4 and 175.9 by combining the adsorption selectivity IAST.
Therefore, the synthesis method for rapidly preparing the sulfonic-group regular mesoporous carbon provided by the patent can obtain the ammonia adsorbent with a high specific surface area, overcomes the complex steps of the traditional preparation method, further reduces the synthesis cost, and has excellent ammonia selective adsorption performance, thereby promoting the industrial scale-up production and application of the sulfonic-group regular mesoporous carbon.
Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A preparation method of sulfonic group regular mesoporous carbon is characterized by comprising the following steps: the method comprises the following steps:
(1) mechanically and uniformly mixing a block copolymer template agent, a phenolic organic compound and an aldehyde organic compound, and then putting into a ceramic burning boat;
(2) transferring the sample obtained in the step (1) to a tubular furnace, and carbonizing the sample in a nitrogen atmosphere;
(3) mixing the sample obtained in the step (2) with KOH, transferring the mixture into a tubular furnace, and roasting the mixture in a nitrogen atmosphere;
(4) neutralizing the sample obtained in the step (3) with an acid solution, then washing with water to be neutral, and drying to obtain a nitrogen-doped ordered mesoporous carbon material OMC;
(5) and (3) placing the sample obtained in the step (4) in a reaction kettle with a polytetrafluoroethylene substrate, adding concentrated sulfuric acid, sulfonating for 12 hours, washing with deionized water to be neutral, and finally drying in vacuum at 100 ℃ to obtain the sulfonic group regular mesoporous carbon S-OMC.
2. The method of claim 1, wherein: the phenolic organic compound in the step (1) is one or more of m-aminophenol, resorcinol and phloroglucinol, the aldehyde organic compound is one or more of terephthalaldehyde and benzaldehyde, and the block copolymer template agent is F127 or P123; wherein the molar ratio of the phenolic hydroxyl group in the phenolic organic compound to the carbonyl group in the aldehyde organic compound is 1: 0.5-1: 5.
3. The method of claim 1, wherein: and (2) mechanically mixing uniformly, namely, grinding and mixing the mixture in a mortar for 10-20 min.
4. The method of claim 1, wherein: and (3) carbonizing at 700-900 ℃ for 1-3 h.
5. The method of claim 1, wherein: the mass ratio of the sample to KOH in the step (3) is 1:1, the roasting temperature is 700-900 ℃, and the roasting time is 2 hours.
6. The method of claim 1, wherein: the acid solution in the step (4) is 1M HCl, and the drying is carried out for 8-12 h at the temperature of 60 ℃.
7. The method of claim 1, wherein: the volume of the concentrated sulfuric acid in the step (5) is 10-30 mL, and the temperature of the sulfonation reaction is 90-140 ℃.
8. A as inThe sulfonic group regular mesoporous carbon prepared by the preparation method of any one of claims 1 to 7, which is characterized in that: the sulfonic group regular mesoporous carbon has a body-centered cubic mesostructure and a specific surface area of 700-1000 m2The volume is 20-40 meshes.
9. Use of the sulfonic acid group regular mesoporous carbon according to claim 8 in ammonia adsorption.
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