CN113353914B - Method for preparing mesoporous carbon by using minerals as raw materials - Google Patents
Method for preparing mesoporous carbon by using minerals as raw materials Download PDFInfo
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- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 97
- 239000011707 mineral Substances 0.000 title claims abstract description 97
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 title claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000010453 quartz Substances 0.000 claims abstract description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052622 kaolinite Inorganic materials 0.000 claims abstract description 8
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 8
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011028 pyrite Substances 0.000 claims abstract description 8
- 239000010445 mica Substances 0.000 claims abstract description 7
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012066 reaction slurry Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 24
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
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- 239000000203 mixture Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 4
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- 239000003463 adsorbent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 230000002194 synthesizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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Abstract
The method for preparing the mesoporous carbon by taking the novel mineral as the raw material is provided, the novel mineral comprises a crystalline component and an amorphous component, the crystalline component accounts for 78.61% of the mass fraction of the mineral, and the amorphous component accounts for 21.39% of the mass fraction of the mineral; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the mass fraction of the crystalline component; the amorphous substance comprises water, simple substance carbon and organic matters, wherein the simple substance carbon accounts for 95.1 percent of the mass fraction of the amorphous component; the method of the invention comprises the step of removing the crystalline component of the novel mineral with hydrofluoric acid. The novel mineral selected by the method contains carbon and silicon dioxide, the carbon and the silicon dioxide grow and are combined together, the silicon dioxide and other components are removed by hydrofluoric acid, the components after being removed by the hydrofluoric acid form a pore channel in situ, the carbon keeps the original state, a mesoporous carbon structure is integrally formed, and the obtained mesoporous carbon has a proper pore channel size and a uniform pore channel.
Description
Technical Field
The invention relates to the field of inorganic non-metallic materials, in particular to a method for preparing mesoporous carbon by taking novel minerals as raw materials.
Background
Mesoporous materials are materials with a pore size in the range of 2nm to 50 nm. Mesoporous carbon has the advantages of high specific surface area, adjustable pore structure and the like as a mesoporous material, so the mesoporous carbon is paid much attention to, has good thermal stability, good electrical conductivity and strong adsorption capacity, has smaller pore diameter, more concentrated pore structure and higher porosity compared with the traditional porous carbon, and is a good electrode material, adsorbent and catalyst carrier.
At present, the common methods for synthesizing the mesoporous carbon material mainly comprise a catalytic activation method, an organogel carbonization method and a template method. The catalytic activation method is a means for synthesizing mesoporous carbon, but because the catalyst used for catalyzing the activated carbon material is metal-containing salt, part of metal always remains in the mesoporous carbon material, and the prepared material has a plurality of micropores, so that the structure and the size of the mesopores are difficult to regulate. Although the organogel carbonization method does not need to add a metal mixture to synthesize the mesoporous carbon material, the method has complicated steps, the porosity of the synthesized mesoporous carbon material is not high enough, the performance is low, the pore size distribution is wide and is not easy to regulate, and supercritical drying equipment required by experiments is expensive and complex to operate. The template method for synthesizing the mesoporous carbon material needs to use a precursor and a template, wherein the precursor is used for providing a carbon source, and the template is used for forming mesopores. The mesoscopic structure is formed by the action of the template agent on the precursor, then the precursor is converted, and finally the template is removed by methods such as high temperature and the like to obtain the mesoporous carbon material with uniform pore channels, but the conditions such as the template agent, the high temperature and the like are used, and the process is complex.
Disclosure of Invention
The invention provides a method for preparing mesoporous carbon by using novel minerals as raw materials based on the composition of the novel minerals, the novel minerals selected by the method contain carbon and silicon dioxide, the carbon and the silicon dioxide grow and are combined together, the components such as the silicon dioxide and the like are removed by hydrofluoric acid, the components removed by the hydrofluoric acid form pore channels in situ, the carbon keeps the original state, the mesoporous carbon structure is integrally formed, the obtained mesoporous carbon has proper pore channel size and uniform pore channel, and the carbon material can be used as a carrier of an adsorbent and a catalyst by the characteristic adsorption effect of the carbon material on organic matters.
The novel mineral raw material used in the invention is a novel natural mineral found in a place in Jiangxi province, the appearance of the novel mineral is black, the main mineral components are silicon dioxide and carbon, trace organic matters are contained, and the silicon dioxide and the carbon are mutually combined and have a mesoporous structure, so that the novel mineral has great utilization value. According to the invention, the mesoporous carbon can be obtained by removing silicon dioxide and organic matters in the mesoporous carbon.
The technical scheme of the invention is as follows: a method for preparing mesoporous carbon by taking a novel mineral as a raw material, wherein the novel mineral comprises a crystalline component and an amorphous component, the crystalline component accounts for 78.61% of the mass fraction of the mineral, and the amorphous component accounts for 21.39% of the mass fraction of the mineral; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the mass fraction of the crystalline component; the amorphous substance comprises water, simple substance carbon and organic matters, wherein the simple substance carbon accounts for 95.1 percent of the mass fraction of the amorphous component; the method comprises the step of removing crystalline components in the novel mineral with hydrofluoric acid.
Further, the method of the present invention comprises the steps of:
s1, taking the novel mineral, drying, roasting and dispersing to obtain mineral powder;
s2, adding the mineral powder into water, stirring to form slurry, adding hydrofluoric acid into the slurry, and reacting to obtain reaction slurry;
s3, filtering the reaction slurry, washing and filtering the filter cake with deionized water, and repeating washing and filtering operations to obtain a clean filter cake;
s4, adding deionized water into the clean filter cake, adding absolute ethyl alcohol, fully stirring and dispersing, standing for 1-3 min, and taking supernatant;
s5, filtering the supernatant in the step S4, drying the filter cake at 105 ℃, and scattering to obtain the mesoporous carbon.
It can be seen from the steps of the present invention that, in step S1, water and organic matters are removed mainly by drying and baking, hydrofluoric acid is added to remove quartz, pyrite, kaolinite, mica and other components therein, impurity ions generated by the reaction of hydrofluoric acid are removed by repeated washing, and deionized water and absolute ethyl alcohol are removed to obtain a suspension of carbon, thereby obtaining high-purity mesoporous carbon.
Further, in the step S1, the drying and roasting temperature is 280-450 ℃; the dispersion is to disperse the mineral to a particle size of less than 325 mesh.
The roasting temperature is to ensure that organic matters in the hydrofluoric acid are thoroughly removed, and the organic matters are dispersed to a fine particle size to enable subsequent hydrofluoric acid reaction to be quicker and ensure that mineral impurities are removed more cleanly.
Further, in the step S2, adding hydrofluoric acid, and reacting at 0-90 ℃ for 1-10 hours; the mass concentration of the hydrofluoric acid is 10% -40%, and the amount of the hydrofluoric acid solution is more than 5 times of the amount of the mineral substance.
The purpose of the hydrofluoric acid reaction is to remove crystalline components, so that according to the composition of minerals, research on the concentration, the amount and the reaction time of the hydrofluoric acid is an important guarantee for guaranteeing the purity and the porosity of the obtained mesoporous carbon.
Further, the washing and filtering operations are repeated 3 to 5 times in step S3 until no fluoride ion is detected in the filtrate.
Further, in step S1, the baking temperature is 300-400 ℃.
Further, the mass concentration of the hydrofluoric acid in the step S2 is 20% to 30%.
Further, the reaction temperature of the hydrofluoric acid added in the step S2 is 70-80 ℃, and the reaction time is 3-5 h.
Further, the standing time in the step S4 is 2-3 min.
Compared with the prior art, the invention has the advantages that:
the invention uses a natural mineral containing carbon as raw material, the mineral reserves are huge, the performance is stable; the method only removes non-carbon components in the minerals, and keeps the original structure and state of carbon; the mesoporous carbon prepared by the method has the advantages of proper pore channel size and uniform pore channel, and can be used as an adsorbent and a carrier of a catalyst by the characteristic adsorption effect of the carbon material on organic matters.
Compared with other preparation methods, the method provided by the invention has the advantages that the raw materials are natural minerals, the preparation is simpler, the raw materials are rich, the cost is lower, and a new way is provided for preparing mesoporous carbon.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a thermal analysis curve of the novel mineral of the present invention;
FIG. 2 is an X-ray diffraction pattern of the novel mineral of the present invention;
FIG. 3 is a graph and a curve of the novel mineral of the present invention after being dispersed in alcohol, wherein (A) is a Scanning Electron Microscope (SEM) with a magnification (Mag) of 20.00KX, and (B) is a SEM with a magnification (Mag) of 1.00 KX; (C) is the X-ray energy spectrum in the square frame line area in the graph (B); (D) is a table of element mass percent and atom percent;
FIG. 4 is a scanning electron micrograph of the novel mineral of the invention after ultrasonic cleaning treatment, wherein (A) the magnification (Mag) is 5.40KX, and B) the magnification (Mag) is 6.00 KX;
FIG. 5 is a scanning electron micrograph of mesoporous carbon prepared according to an embodiment of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings and the detailed description of the invention.
Research on novel mineral composition
The novel mineral is obtained from Fengcheng county in Yichun city, Jiangxi province and is black. The component research method and the specific process are as follows.
First, thermal analysis
The atmosphere for the thermal analysis of the sample was air, and the sample was loaded using a Pt crucible as the sample stage. TG, DTG and DSC curves of the sample were obtained at a temperature rise rate of 10 ℃/min as shown in FIG. 1. The image clearly shows that there are two main decomposition stages of the mineral during the temperature rise to 1000 ℃. The first stage of sample decomposition is at 25 ℃ to 200 ℃, which appears as a bulge on the DSC curve, as an endothermic reaction. This stage involves both the evaporation of a small amount of water from the sample and the dehydroxylation of the sample. As can be seen from the analysis of the image data in fig. 1, the mass percentage of water and hydroxyl groups contained in the sample was 1.05%. The second stage of decomposition of the sample is between 420 ℃ and 720 ℃, which is represented by a depression on the DSC curve, is an exothermic reaction, mainly associated with oxidation and combustion of carbon within the sample. The peak value of the exothermic peak at the stage is 625.9 ℃ as can be seen from the DSC curve, namely the oxidation rate of carbon in the sample is maximum at the temperature, and the exothermic quantity can reach 7.531 mW/mg. Meanwhile, the DTG curve shows that the mass percent change rate of the sample reaches the fastest value of-2.17%/min at 620.7 ℃. The loss on ignition ratio is calculated by a TG curve, and the loss of the mass percent of the sample at the stage is 20.34 percent, namely the sample contains the simple substance carbon with corresponding proportion.
Two, X-ray diffraction analysis
The X-ray diffraction analysis (XRD) mainly aims at the analysis of crystalline substances in minerals, and the components of the crystalline substances in the minerals and the content of each component can be obtained by analyzing diffraction peaks of an XRD pattern. The invention carries out X-ray diffraction scanning on a mineral sample with the 2 theta of 10-80 degrees to obtain a graph 2, and the graph 2 can determine that: crystalline substances within minerals are quartz, kaolinite, gypsum and pyrite.
By further analysis of the XRD pattern in fig. 2, the crystal planes having miller indices (001), (100), (101), (200), (004), (104), (213), (204), (312), (223), (204), (223), (202), (311), (314), (321), (206) can be identified from the diffraction peaks in the pattern. Through comparison with an open database, the components of the product can be respectively quartz, pyrite, kaolinite and mica. The content of each component can be calculated by analyzing the intensity of the diffraction peak, and the mass fraction of each component is shown in table 1.
TABLE 1 compositions and mass fractions of crystalline substances in novel minerals
| Components | Quartz | Pyrite | Kaolinite | Mica |
| Mass fraction of | 91％ | 4％ | 4％ | 1％ |
It can be seen that the crystalline component of the mineral is mainly quartz, with small amounts of pyrite, kaolinite and mica as impurities.
Third, microscopic analysis
Microscopic analysis mainly uses a combination of Scanning Electron Microscopy (SEM) and X-ray energy spectroscopy (EDS) to test the structure and element distribution of a sample. The test samples are raw mineral ores and treated mineral samples, and the treatment methods of the minerals comprise ultrasonic cleaning, high-temperature decarbonization, chemical decarbonization and chemical silica removal. By observing the above five test samples, it is possible to comprehensively analyze the microscopic composition of the minerals and investigate the suitability of the corresponding treatment method.
First, the morphology of the raw ore was observed using SEM, and the element content thereof was analyzed using EDS. In order to observe the mineral without destroying its basic structure, the mineral was dispersed in alcohol as it is, and the dispersion was simply shaken and then dropped on an aluminum foil to prepare a scanning electron microscope sample for observation. As shown in fig. 3(a) and (B), the mineral is stacked from a plurality of fragments, and there are a large number of voids and holes. These bulk structures have rounded depressions and streaks on their surface, which may be due to bio-etching. In addition to the massive structure, a large number of rods are present on the surface of the mineral, with diameters of 50-100nm and lengths of 500nm-1 μm.
Further EDS spectrum analysis was performed on the region in the block diagram in fig. 3(B), resulting in fig. 3(C) and fig. 3 (D). Since the penetration depth of the X-ray spectral analysis is 1.5 μm, the elemental analysis is mainly performed on the surface layer of the sample. As can be seen from fig. 3(C), the main elements in the mineral are C, O, Al and Si, wherein the C content is the highest and accounts for 42.51% by mass, and the Al content is the lowest and accounts for 4.64% by mass.
The mass percentage of the C element obtained by EDS energy spectrum scanning is far higher than 20.34% by combining the results of thermal analysis and XRD, and the carbon element is mainly enriched on the surface of the mineral or in some special structures, but is not uniformly distributed in the mineral structure. Wherein carbon and quartz grow together, and mesoporous carbon can be obtained by removing silicon dioxide and the like.
In order to observe the inner layer structure of the mineral more carefully and clearly, the invention uses the ultrasonic cleaning method to separate the scraps and impurities on the surface of the mineral particles, the mineral sample is dispersed in alcohol, ultrasonic cleaning is carried out for 15min, and the sample is dripped on a silicon wafer to prepare a scanning electron microscope sample for observation, the obtained scanning electron microscope image is shown in figure 4, after the ultrasonic cleaning, the scraps and rod-shaped objects on the surface of the mineral are basically eliminated, and the ultrasonic cleaning is also shown to be capable of effectively separating the scraps and impurities on the surface of the mineral. Fig. 4(a) shows that there are circular depressions of varying sizes on the mineral particles and that there are mesoporous and microporous structures. Fig. 4(B) also shows that there are rounded depressions on the mineral particles and that there are nicks and cracks.
Fourthly, analysis of specific surface area and pore space
The specific surface area and pore size analysis is mainly to detect the specific surface area of a sample and the pore structure of the sample by using a specific surface area and pore size analyzer. The algorithm used for the detection is mainly BET. The test sample was as-mineral, and after drying the sample at 115 ℃, the BET specific surface area test was performed using nitrogen as an adsorbate.
The BET specific surface area of the mineral obtained as such was tested to be 5.2684m2Per g, total pore volume 0.028110cm3The adsorption average pore diameter is 213.421 angstroms, and the desorption average pore diameter is 201.633 angstroms.
In conclusion, the novel mineral comprises a crystalline component and an amorphous component, wherein the crystalline component accounts for 78.61% of the mass fraction of the mineral, and the amorphous component accounts for 21.39% of the mass fraction of the mineral; the mesoporous carbon is prepared by removing quartz and impurities in the quartz, wherein the crystalline components comprise 91% of quartz, the amorphous substances comprise water, simple substance carbon and organic substances, the content of carbon is 20.34%, and the carbon and the quartz grow together.
Example 1
1. Taking novel minerals as raw materials, drying and roasting for 4 hours at 280 ℃ until no trace organic matters exist in the novel minerals, and scattering the novel minerals to obtain dry mineral powder;
2. adding the dried mineral powder into water, stirring to form slurry, adding hydrofluoric acid with the mass concentration of 10%, and reacting at 20 ℃ for 10 hours to obtain reaction slurry;
3. filtering the reaction slurry, taking a filter cake, washing and filtering the filter cake by deionized water, and repeating the step for 4 times until no fluorine ions are detected in the solution to obtain the filter cake;
4. adding deionized water into the washed filter cake, adding 2% absolute ethyl alcohol, fully stirring and dispersing, standing for 1min, and taking supernatant;
5. and filtering the supernatant, taking a filter cake, drying and scattering to obtain the mesoporous carbon.
Measuring the specific surface of the obtained mesoporous carbonProduct of 2641.5742m2(iv) total pore volume of 2.62354cm3/g。
Example 2
1. Taking novel minerals as raw materials, drying and roasting for 4h at 450 ℃ until no trace organic matters exist in the novel minerals, and scattering the novel minerals to obtain dry mineral powder;
2. adding the dried mineral powder into water, stirring to form slurry, adding hydrofluoric acid with the mass concentration of 40%, and reacting at 90 ℃ for 1 h;
3. filtering the slurry after the reaction is finished, taking a filter cake, washing and filtering the filter cake by deionized water, and repeating the step for 4 times until no fluorine ions are detected in the solution;
4. adding deionized water into the washed filter cake, adding 2% absolute ethyl alcohol, fully stirring and dispersing, standing for 5min, and taking supernatant;
5. and filtering the supernatant, taking a filter cake, drying and scattering to obtain the mesoporous carbon.
The specific surface area of the obtained mesoporous carbon is measured to be 2673.3542m2Per g, total pore volume 2.6837cm3/g。
Example 3
1. Taking Fengcheng soil of Fengcheng county in Yichun city, Jiangxi province as a raw material, drying and roasting the raw material at 300 ℃ for 4 hours until no trace organic matter exists, and scattering the raw material to obtain dry Fengcheng soil powder;
2. adding the dried Fengcheng soil powder into water, stirring to form slurry, adding hydrofluoric acid with the mass concentration of 30% into the slurry, and reacting for 5 hours at 80 ℃;
3. filtering the slurry after the reaction is finished, taking a filter cake, washing and filtering the filter cake by deionized water, and repeating the step for 4 times until no fluorine ions are detected in the solution;
4. adding deionized water into the washed filter cake, adding 2% absolute ethyl alcohol, fully stirring and dispersing, standing for 3min, and taking supernatant;
5. and filtering the supernatant, taking a filter cake, drying and scattering to obtain the mesoporous carbon. The specific surface area of the obtained mesoporous carbon is measured to be 2716.2358m2(iv) total pore volume of 2.7286cm3/g。
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for preparing mesoporous carbon by using minerals as raw materials is characterized in that,
the mineral comprises a crystalline component and an amorphous component, wherein the crystalline component accounts for 78.61% of the mass fraction of the mineral, and the amorphous component accounts for 21.39% of the mass fraction of the mineral; the crystalline component comprises quartz, pyrite, kaolinite and mica, wherein the quartz accounts for 91% of the mass fraction of the crystalline component; the amorphous substance comprises water, simple substance carbon and organic matters, wherein the simple substance carbon accounts for 95.1 percent of the mass fraction of the amorphous component;
the method comprises the step of removing crystalline components in the mineral with hydrofluoric acid.
2. The method for preparing mesoporous carbon from minerals according to claim 1, comprising the following steps:
s1, taking the minerals, drying, roasting and dispersing to obtain mineral powder;
s2, adding the mineral powder into water, stirring to form slurry, adding hydrofluoric acid into the slurry, and reacting to obtain reaction slurry;
s3, filtering the reaction slurry, washing and filtering the filter cake with deionized water, and repeating washing and filtering operations to obtain a clean filter cake;
s4, adding deionized water into the clean filter cake, adding absolute ethyl alcohol, fully stirring and dispersing, standing for 1-3 min, and taking supernatant;
s5, filtering the supernatant in the step S4, drying the filter cake at 105 ℃, and scattering to obtain the mesoporous carbon.
3. The method for preparing mesoporous carbon from minerals as claimed in claim 2, wherein the baking and roasting temperature in step S1 is 280-450 ℃; the dispersion is to disperse the mineral to a particle size of less than 325 mesh.
4. The method for preparing mesoporous carbon from minerals as claimed in claim 2, wherein in step S2, the reaction temperature is 0-90 ℃ after hydrofluoric acid is added, and the reaction time is 1-10 h; the mass concentration of the hydrofluoric acid is 10% -40%, and the amount of the hydrofluoric acid solution is more than 5 times of the amount of the mineral substance.
5. The method for preparing mesoporous carbon using minerals as raw materials according to claim 2, wherein the washing and filtering operations are repeated 3 to 5 times in step S3 until no fluoride ion is detected in the filtrate.
6. The method for preparing mesoporous carbon from minerals as claimed in claim 2 or 3, wherein the baking and roasting temperature in step S1 is 300-400 ℃.
7. The method for preparing mesoporous carbon from minerals as claimed in claim 2 or 4, wherein the concentration of hydrofluoric acid in step S2 is 20% -30% by mass.
8. The method for preparing mesoporous carbon from minerals as claimed in claim 2 or 4, wherein the reaction temperature of the S2 after adding hydrofluoric acid is 70-80 ℃, and the reaction time is 3-5 h.
9. The method for preparing mesoporous carbon from minerals as claimed in claim 2, wherein the standing time in step S4 is 2-3 min.
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