CN114433055B - Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof - Google Patents
Carbon catalyst with highly-open hierarchical pore structure and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 238000001694 spray drying Methods 0.000 claims abstract description 20
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
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- 239000007833 carbon precursor Substances 0.000 claims abstract description 11
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- 238000002156 mixing Methods 0.000 claims abstract description 4
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- 235000019795 sodium metasilicate Nutrition 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001805 chlorine compounds Chemical group 0.000 claims description 3
- 229960002442 glucosamine Drugs 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
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- 239000003575 carbonaceous material Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 13
- 229940039790 sodium oxalate Drugs 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006385 ozonation reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
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- 239000010431 corundum Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 230000008018 melting Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
- B01J35/618—Surface area more than 1000 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/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
- B01J35/63—Pore volume
- B01J35/638—Pore volume 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention provides a preparation method of a carbon catalyst with a highly open hierarchical pore structure, which comprises the following steps: dissolving a carbon precursor and a double-salt template agent in an alkali solution, and then stirring and mixing at room temperature to obtain a precursor solution; spray drying the precursor solution to obtain microsphere powder with a unique form, wherein the temperature of the top of the tower in the spray drying process is 150-200 ℃; calcining the microsphere powder in an inert atmosphere at the calcining temperature of 600-1000 ℃; the salt templating agent was removed by washing with water to obtain a carbon catalyst having a highly open hierarchical pore structure. The carbon catalyst prepared by combining the double-salt template method with the spray drying technology has excellent catalytic performance on the ozone oxidation reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon catalyst with a highly open hierarchical pore structure, a preparation method and application thereof, in particular to a carbon catalyst with a highly open hierarchical pore structure and application thereof in the field of catalytic oxidation of ozone.
Background
The hierarchical porous carbon material has great potential in the aspects of energy storage and conversion, heterogeneous catalysis, adsorption, separation and life science application. In recent years, remarkable progress is made in the design and synthesis of such materials, and salt templates have been widely used in the synthesis of hierarchical porous carbon materials due to their advantages of low price, abundant varieties, easy removal, and the like.
At present, in the research on the preparation of the hierarchical porous carbon material by using a salt template method, the prepared hierarchical porous carbon materials have low specific surface area and low contents of mesopores and macropores, so that in the process of catalytically degrading organic pollutants in a water body, the pollutants are difficult to diffuse and transfer to active sites in the carbon material, and the utilization rate of the active sites of the carbon catalyst is low. In order to improve the catalytic performance of the catalyst by enhancing the mass transfer diffusion of the reaction substrate, researchers have conducted intensive studies on the preparation of carbon catalysts having highly open hierarchical pore structures.
The current commonly used method is as follows: 1. the salt template is combined with the hard template or the soft template to obtain an open hierarchical pore structure, but toxic and harmful reagents are needed in the preparation process, and the cost of raw materials is overhigh; 2. the porosity and pore size distribution of the target hierarchical porous carbon material are regulated and controlled by using a multiple salt template, namely by using the principle that the grain sizes of different crystal salts are different, but the performance of the porous carbon material obtained by the prior art needs to be further improved.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a carbon catalyst with a highly open hierarchical pore structure by coupling a double salt template method with a spray drying technology, and the hierarchical pore carbon material prepared by the method has excellent catalytic performance in an ozone catalytic oxidation reaction.
The present invention provides a method for preparing a carbon catalyst having a highly open hierarchical pore structure, comprising the steps of:
(1) Uniformly mixing a carbon precursor, a double-salt template agent and an alkali solution to obtain a precursor solution;
(2) Carrying out spray drying on the precursor solution to obtain microsphere powder;
(3) Calcining the microsphere powder for the first time to obtain a calcined product;
(4) And washing and drying the calcined product to obtain the carbon catalyst with a highly open hierarchical pore structure.
Preferably, the total solid content of the precursor solution is 6-14 wt%.
Preferably, the carbon precursor is selected from one or more of glucosamine and salts thereof, glycine and sucrose.
Preferably, the double-salt template is chloride and sodium metasilicate.
Preferably, the mass ratio of the carbon precursor to the chloride to the sodium metasilicate is 1 (3-6): (0.25-0.75).
Preferably, the chloride is selected from potassium chloride and/or sodium chloride.
Preferably, the temperature of the top of the spray drying tower is 150-200 ℃.
Preferably, the temperature of the primary calcination is 600 to 800 ℃.
Preferably, the method further comprises the following steps after the primary calcination:
carrying out secondary calcination on the product after the primary calcination to obtain a calcined product;
the temperature of the secondary calcination is 600-1000 ℃.
The invention provides a carbon catalyst with a highly open hierarchical pore structure, which is prepared by the method in the technical scheme and has the specific surface area of 1208-2611 m 2 Per gram, pore volume of 0.94-1.63 cm 3 The oxygen content is 12.39-25.38 wt%.
In yet another aspect, the present invention provides an ozone oxidation catalyst comprising:
the carbon catalyst with the highly-open hierarchical pore structure is prepared by the method in the technical scheme.
Although many double-salt templates and multi-salt templates have been developed in the prior art, many mixed-salt templates do not have high melting temperatures (the melting temperature of the mixed-salt templates is generally lower than that of a single component), and the invention finds that the salt templates with high melting temperatures can maintain the original morphology of particles in the calcining process, which plays an important role in improving the specific surface area and oxygen content of carbon materials and forming a three-dimensional hierarchical pore structure.
By means of the technical scheme, the invention at least has the following advantages:
the invention utilizes the spray drying technology, the conversion from atomized small droplets to dried microspheres only needs 0-2 s, and the limited domain co-assembly of the carbon precursor and the double-salt template agent can be realized in the micro-droplets in the drying process, which plays an important role in improving the specific surface area and the oxygen content and forming a highly open multi-level pore structure; meanwhile, the double-salt template used by the invention can be easily removed by washing and oscillation, and the salt template can be recovered by drying the washing liquid, so that the recycling of the salt template is realized.
The invention provides a method for preparing a carbon catalyst with a highly open hierarchical pore structure by coupling a double-salt template method with a spray drying technology, the method is simple in process flow, low in cost and suitable for industrial production, and the hierarchical pore carbon material prepared by the method has excellent catalytic performance in an ozone oxidation reaction.
Drawings
FIG. 1 is a SEM test result of a spray dried product of example 1 of the present invention;
FIG. 2 is a SEM test result of a carbon material prepared in example 1 of the present invention;
FIG. 3 is a SEM test result of a carbon material prepared in comparative example 1 of the present invention;
FIG. 4 shows N in carbon materials obtained in examples 1 to 4 of the present invention and comparative example 1 2 Adsorption and desorption isotherms and pore size distribution maps;
FIG. 5 shows the results of analyzing the element content of the carbon materials prepared in examples 1 to 3 of the present invention and comparative example 1 (quantitatively analyzed using a Thermo Fisher Scientific flash CHNS/O element analyzer);
FIG. 6 shows the results of the tests of the carbon materials prepared in examples 1-4 of the present invention and comparative example 1 for catalyzing the oxidation of sodium oxalate by ozone.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a carbon catalyst with a highly-open hierarchical pore structure, which comprises the following steps:
(1) Uniformly mixing a carbon precursor, a double-salt template agent and an alkali solution to obtain a precursor solution;
(2) Carrying out spray drying on the precursor solution to obtain microsphere powder;
(3) Calcining the microsphere powder for the first time to obtain a calcined product;
(4) And washing and drying the calcined product to obtain the carbon catalyst with a highly open hierarchical pore structure.
In the present invention, the carbon precursor may be selected from one or more of glucosamine and salts thereof, glycine, and sucrose.
In the invention, the double-salt template agent is chloride and sodium metasilicate.
In the present invention, the chloride may be selected from potassium chloride and/or sodium chloride.
In the present invention, the alkali in the alkali solution may be selected from sodium hydroxide and/or potassium hydroxide.
In the present invention, the mass concentration of the alkali solution may be 0 to 0.5mol/L (not including 0), 0.1 to 0.3mol/L, or 0.2mol/L.
In the present invention, the total solid content of the precursor solution may be 6 to 14wt%, or 8 to 12wt%, or 10wt%, or preferably 12wt%.
In the present invention, the mass ratio of the carbon precursor, the chloride, and the sodium metasilicate may be 1: (3-6): (0.25 to 0.75) and may be in the range of 1:4: (0.25-0.75) and may be in the range of 1:4:0.5.
in the present invention, the precursor liquid in the material tank can be broken into uniform small droplets by the micro-fluidic aerosol nozzle by using compressed air in the spray drying process.
In the invention, the temperature of the top of the spray drying tower can be 150-200 ℃, 160-190 ℃, 170-180 ℃ and preferably 170 ℃.
In the present invention, the pressure during the spray-drying process may be 0.1 to 0.5kg/cm 2 And may be 0.2 to 0.4kg/cm 2 And may be 0.3kg/cm 2 (ii) a The working vibration frequency of the atomizer can be 5-15 kHz, also can be 8-12 kHz, and is preferably 10kHz; the amplitude value can be 10-20 Vpp, and can also be 12-16 Vpp, preferably 15Vpp; the flow rate of the hot air can be 250-350L/min, 280-320L/min and 300L/min.
In the invention, the particle size of the dry microsphere powder can be regulated and controlled by changing the size of a nozzle and the air speed used in the spray drying process.
In the invention, as long as the spray drying condition is kept constant, the property of the obtained dry microsphere powder is kept unchanged, the spray drying device is very easy to operate, can continuously feed, has high drying speed and high yield, and is suitable for industrial large-scale production.
In the present invention, the primary calcination may be carried out by charging the spray-dried microsphere powder into a corundum ark in a tube furnace.
In the present invention, the primary calcination may be performed in an inert atmosphere, which may be argon and/or nitrogen.
In the invention, the temperature of the primary calcination can be 600-800 ℃, can also be 700-800 ℃, and is preferably 750 ℃; the time of the primary calcination can be 2-4 h, and can also be 3h.
In the invention, the temperature can be increased from room temperature to the primary calcination temperature (600-800 ℃) at the temperature increase rate of 2-5 ℃/min in the primary calcination process; the heating rate can also be 3-4 ℃/min.
In the present invention, the primary calcination may further include:
and carrying out secondary calcination on the product after the primary calcination to obtain a calcined product.
In the invention, the parameter selection range of the secondary calcination can be consistent with the parameter selection range of the primary calcination in the technical scheme, and can also be other parameter ranges; the temperature of the secondary calcination can be 600-1000 ℃.
In the invention, the double-salt template agent can be removed by water washing to obtain the carbon catalyst with a highly open hierarchical pore structure; the water wash may be a shaking of the shake table to remove the double salt template.
In the present invention, the method of washing with water may be: and soaking the calcined product in water for constant-temperature oscillation, and then filtering, washing and drying to obtain the carbon catalyst.
In the present invention, the water may be ultrapure water; the calcined product may be put into a glass container containing ultrapure water; the constant temperature oscillation may be performed in a constant temperature oscillator; the constant-temperature oscillation time can be 2-4 h or 3h; the filtration can be vacuum filtration; the washing may be washing with ultrapure water to completely remove salt components in the carbon material; the drying temperature can be 50-70 ℃, 55-65 ℃ or 60 ℃; the drying method can be vacuum drying or normal pressure drying.
In the present invention, after the water washing, the method may further include: the double-salt template agent is recovered by drying the water washing liquid, so that the cyclic utilization of the salt template agent is realized. The drying method may be oven drying.
The invention provides a carbon catalyst with a highly open hierarchical pore structure, which is prepared by the method in the technical scheme, and the specific surface area of the carbon catalyst can be 1208-2611 m 2 Per g, pore volume may be 0.94-1.63 cm 3 The oxygen content may be 12.39 to 25.38 wt.%.
The present invention provides an ozone oxidation catalyst comprising:
the carbon catalyst with the highly-open hierarchical pore structure is prepared by the method in the technical scheme.
The ozone oxidation catalyst can be used for catalyzing ozone oxidation reaction, such as catalyzing ozone to oxidize sodium oxalate.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to be implemented in accordance with the content of the specification, the following detailed description is made of preferred embodiments of the present invention in conjunction with the accompanying drawings. The following examples are provided to illustrate the present invention and are not intended to limit the scope of the present invention.
Example 1
6g of glucosamine hydrochloride, 24g of potassium chloride and 3g of sodium metasilicate are weighed and added into 0.2mol/L sodium hydroxide aqueous solution, and the mixture is stirred for 4 hours at room temperature, wherein the total solid content of the precursor solution is 12wt%. Pouring the precursor liquid into a polytetrafluoroethylene material tank, utilizing compressed air to break the precursor liquid in the material tank into uniform small droplets through a microfluidic aerosol nozzle, and carrying out spray drying on the precursor liquid under the conditions that the tower top temperature is 170 ℃ and the hot air flow rate is 300L/min.
And (3) putting the collected dry powder into a corundum ark, putting the corundum ark into a tube furnace for calcination, heating the corundum ark to a corresponding temperature of 750 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, and keeping the temperature for 2 hours. And then, soaking the calcined sample in a glass container containing ultrapure water, placing the glass container into a constant-temperature oscillator for oscillation for 3 hours, then carrying out vacuum filtration, washing the glass container with a certain amount of ultrapure water to completely remove salt components in the carbon material, and finally carrying out vacuum drying on the carbon material at 60 ℃ overnight to obtain the carbon catalyst with the highly-open hierarchical pore structure.
FIG. 1 shows SEM test results of samples after spray drying of example 1 of the present invention, and it can be seen that the surface of the dried microspheroidal particles exhibit rhombic folds, which are caused by some angular protrusions of crystals of potassium chloride and sodium metasilicate, and the interior of the particles exhibit a semi-solid structure.
Fig. 2 is SEM test results of the carbon material obtained after the calcination, water washing, and drying processes in example 1 of the present invention, and it can be seen that the sample has a three-dimensional network structure after the calcination at 750 ℃, and the pore structure is particularly developed.
Example 2
A carbon catalyst having a highly open hierarchical pore structure was prepared according to the method of example 1, except that the mass of glucosamine hydrochloride was 6g, the mass of potassium chloride was 24g, and the mass of sodium metasilicate was 1.5g.
Example 3
A carbon catalyst having a highly open hierarchical pore structure was prepared according to the method of example 1, except that the mass of glucosamine hydrochloride was 6g, the mass of potassium chloride was 24g, and the mass of sodium metasilicate was 4.5g.
Example 4
A carbon catalyst having a highly open hierarchical pore structure was prepared according to the method of example 1, except that the resulting carbon material was subsequently subjected to secondary calcination by: heating to 1000 ℃ at a heating rate of 5 ℃/min under argon atmosphere and keeping for 2h.
Comparative example 1
A carbon material was prepared according to the method of example 1, except that sodium metasilicate was not added, as in example 1.
Fig. 3 is SEM test results of the carbon material obtained by calcining, washing and drying comparative example 1 of the present invention, and it can be seen that the spherical morphology of the microsphere powder obtained by spray-drying the precursor solution without sodium metasilicate after calcining at 750 ℃ is still maintained, but the pore structure is not developed.
Performance detection
Carbon materials prepared in examples 1 to 4 of the present invention and comparative example 1 were subjected to N 2 Detecting adsorption and desorption isotherms and pore size distribution, wherein the detection method comprises the following steps: this was measured by using a Micromeritics ASAP2020 instrument at-196 ℃.
The results are shown in FIG. 4 and the following table, in which the data are shown in pairs N 2 The result obtained by the adsorption and desorption isotherm calculation, S BET Refers to the specific surface area, V, of the material calculated according to the BET model total Is the pore volume of the material.
| S BET (m 2 /g) | V total (cm 3 /g) | |
| Example 1 | 2035 | 1.09 |
| Example 2 | 1819 | 1.47 |
| Example 3 | 1944 | 1.12 |
| Example 4 | 2611 | 1.63 |
| Comparative example 1 | 2000 | 0.94 |
As can be seen from fig. 4 and the above table, the carbon catalyst obtained using the single salt template differs significantly in pore structure from that obtained using the double salt template. Comparing the pore size distribution curves of the carbon catalysts prepared in example 2 and comparative example 1, it was found that the introduction of sodium metasilicate has a great promoting effect on the generation of large mesopores.
Fig. 5 is a result of analyzing the element content of the carbon materials prepared in examples 1 to 3 and comparative example 1, and it can be seen that the introduction of sodium metasilicate inhibits the decomposition of the oxygen-containing functional groups of the material to some extent, thereby increasing the oxygen content of the carbon material, as compared to the oxygen content of the carbon material prepared without adding sodium metasilicate.
Example 5 catalytic ozonation of sodium oxalate
The carbon materials prepared in examples 1 to 4 and comparative example 1 were used as catalysts for catalyzing ozone oxidation of sodium oxalate, and the ozone oxidation and catalytic ozone oxidation processes were carried out in a two-necked flask in a semi-batch mode by the following specific methods:
adding 100mL of 50ppm sodium oxalate solution and 20mg of catalyst into a reactor, stirring by using a magnetic stirrer, preparing ozone from dry high-purity oxygen (18 mL/min) by using an ozone generator, wherein the concentration of gas-phase ozone is 50ppm, and continuously introducing the ozone into the sodium oxalate solution; taking water sample in a certain period, immediately passing through the membrane, and then adding quenching agent Na 2 S 2 O 3 And (4) stopping the oxidation-reduction reaction in the water sample (quenching the residual ozone in the water sample).
Determination of sodium oxalate content in Water samples by ion chromatography (ICS-600, sammer Feishell science Co., ltd.) with Na 2 CO 3 /NaHCO 3 As the mobile phase, the mobile phase velocity was 0.8mL/min.
Comparative example 2
The catalytic ozonation of sodium oxalate was carried out according to the method of example 5, differing from example 5 in that no catalyst was added.
Fig. 6 is a graph showing that different carbon materials catalyze the degradation of sodium oxalate through ozonation, and it can be seen that, compared with the case of singly using sodium oxalate through ozonation (comparative example 2), the degradation of sodium oxalate is obviously accelerated after the catalyst is added, and the removal rate of sodium oxalate through ozonation alone is increased from less than 10% to 100%, which indicates that the catalyst prepared by the invention has excellent catalytic activity in catalyzing the degradation of sodium oxalate through ozonation.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitutions or changes made by the person skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the invention is subject to the claims.
While the invention has been described and illustrated with reference to specific embodiments thereof, these descriptions and illustrations do not limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (9)
1. A method for preparing a carbon catalyst having a hierarchical pore structure, comprising the steps of:
(1) Uniformly mixing a carbon precursor, a double-salt template agent and an alkali solution to obtain a precursor solution;
(2) Carrying out spray drying on the precursor solution to obtain microsphere powder;
(3) Calcining the microsphere powder for the first time to obtain a calcined product;
(4) Washing and drying the calcined product to obtain the carbon catalyst with the hierarchical pore structure;
the double-salt template agent is chloride and sodium metasilicate;
the mass ratio of the carbon precursor to the chloride to the sodium metasilicate is 1: (3 to 6): (0.25 to 0.75).
2. The method according to claim 1, wherein the total solid content of the precursor liquid is 6 to 14wt%.
3. The method of claim 1, wherein the carbon precursor is selected from one or more of glucosamine and salts thereof, glycine, and sucrose.
4. The process according to claim 1, characterized in that the chloride is selected from potassium chloride and/or sodium chloride.
5. The method according to claim 1, wherein the spray drying has an overhead temperature of 150 to 200 ℃.
6. The method according to claim 1, wherein the temperature of the primary calcination is 600 to 800 ℃.
7. The method of claim 1, further comprising, after the primary calcination:
carrying out secondary calcination on the product after the primary calcination to obtain a calcined product;
the temperature of the secondary calcination is 600 to 1000 ℃.
8. A carbon catalyst having a hierarchical pore structure, which is prepared by the method according to claim 1, and has a specific surface area of 1208 to 2611m 2 (g) pore volume of 0.94 to 1.63cm 3 The oxygen content is 12.39 to 25.38wt%.
9. An ozone oxidation catalyst comprising:
a carbon catalyst having a hierarchical pore structure prepared by the process of claim 1.
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| CN111453712A (en) * | 2019-01-21 | 2020-07-28 | 金华晨阳科技有限公司 | Hollow carbon ball with multistage pore structure and preparation method thereof |
| CN111606408A (en) * | 2020-06-22 | 2020-09-01 | 苏州大学 | Application of shaddock peel biochar in catalytic ozonation degradation of organic pollutants in wastewater |
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| CN111453712A (en) * | 2019-01-21 | 2020-07-28 | 金华晨阳科技有限公司 | Hollow carbon ball with multistage pore structure and preparation method thereof |
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