CN110975871A - Mesoporous carbon material-loaded cobalt-based catalyst and preparation method thereof - Google Patents
Mesoporous carbon material-loaded cobalt-based catalyst and preparation method thereof Download PDFInfo
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Images
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J35/393—
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- B01J35/615—
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- B01J35/633—
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- B01J35/647—
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a mesoporous carbon material-loaded cobalt-based catalyst and a preparation method thereof, belonging to the technical field of metal catalysts. The preparation method of the cobalt-based catalyst comprises the following steps: (1) mixing Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol solution; (2) immersing the mesoporous carbon material GMC into the solution in the step (1), and then performing rotary evaporation on the solutionEvaporating to obtain a mixture; (3) putting the mixture obtained in the step (2) into an oven for drying; then calcining to obtain the catalyst. The catalyst has higher graphitization degree, more uniform dispersion of CoO particles, higher CO conversion rate and lower CO2Rate of formation, and C5+The selectivity of (A) is better.
Description
Technical Field
The invention relates to a cobalt-based catalyst loaded by a mesoporous carbon material and a preparation method thereof, belonging to the technical field of metal catalysts.
Background
Since the industrial revolution, the demand of human beings for energy is increasing, and the limited nature of non-renewable resources such as oil and coal forces people to seek new energy, such as nuclear energy, wind energy and solar energy, are the hot topics of research and discussion. Among them, biomass is one of the core topics, and it has the advantages of wide sources, various varieties, great development potential, etc. People convert biomass into fuel, electric energy and the like by utilizing the biomass, so that the energy problem is solved, and some waste biomass can be recycled.
The porous carbon material not only has the advantages of the carbon material such as acid and alkali resistance, high temperature resistance, stable chemical property, low price and the like, but also has the excellent properties of regular pore channel structure, large specific surface area, adjustable pore diameter and the like.
At present, the porous carbon material prepared by using a hard template method has higher specific surface area, pore volume and large pore diameter, but the porous carbon material also has certain limitations in practical application, such as: the prepared material replicates the structure of the templating agent but cannot be changed at will.
In the Fischer-Tropsch catalytic reaction, the selection of the carrier is closely related to the catalytic performance of the catalyst. Too strong interaction between the carrier and the metal affects the dispersion performance of the metal and is not beneficial to the reduction of the metal; otherwise, the stability of the metal is reduced.
Currently, the active phase of cobalt-based catalysts for the fischer-tropsch reaction is elemental cobalt. Obtaining highly dispersed and highly reduced elemental cobalt particles on the surface of the catalyst is the key to improving the reaction efficiency of the cobalt-based catalyst. To increase the dispersion of cobalt species, many research efforts have been directed to using supports such as TiO with high specific surface area and well-developed pores2、Al2O3、SiO2Etc. to carry the activityAnd (4) components. However, the carrier and the active component are easy to form species which are difficult to reduce, so that an active phase with high dispersity and high reduction degree which are unified is difficult to obtain on the surface of the catalyst.
Disclosure of Invention
In order to solve at least one of the above problems, the present invention provides a cobalt-based catalyst supported on a mesoporous carbon material and a method for preparing the same. The catalyst has higher CO conversion rate and better catalytic reaction performance; at C5+The selectivity of the method is obviously improved.
The first purpose of the invention is to provide a preparation method of a mesoporous carbon material, which comprises the following specific steps:
s1: uniformly mixing SBA-15 and soybean oil by adopting a solid-liquid ball milling template method;
s2: transferring the mixture of S1 into a quartz tube furnace, and heating to 700-900 ℃ for carbonization;
s3: and etching the mixture of S2 with NaOH solution to obtain the mesoporous carbon material, and marking as the mesoporous carbon material GMC.
In one embodiment, the mass ratio of SBA-15 to soybean oil mixture described in S1 is 1: 2.
In one embodiment, the mixing manner of S1 is: using a ball mill at 400rpm min-1Ball milling is carried out for 5 hours at a rotating speed.
In one embodiment, the carbonization process of S2 is specifically: in N2Under protection, the heating rate is as follows: 4 ℃ min-1The carbonization time is 5 h.
In one embodiment, the concentration of the NaOH solution in S3 is 2 mol/L.
In one embodiment, the number of etching times in S3 is 3, and each etching time is 24 h.
In one embodiment, the preparation method of SBA-15 comprises: first, 3.0g of surfactant P123 and 3.0g of glycerol were mixed, and then added to 115.0mL of a dilute hydrochloric acid solution (1.5 mol.L)-1) Stirring the mixture in a water bath kettle at 37 ℃ for transparency, stirring the mixture vigorously after 3 hours, dropwise adding 6.45g of diethyl orthosilicate (TEOS) dropwise, and stirring vigorously for 5min after the addition is finished; then the mixed solution is added inStanding in a water bath at 37 ℃ for 24h, taking out the mixture and putting the mixture into an oven at 110 ℃ for 12 h; cooling to room temperature, repeatedly performing suction filtration and washing on the obtained white solid until the pH value is 7, then washing the white solid for 2-3 times by using absolute ethyl alcohol, then putting the product into an oven at 80 ℃ for drying, and then putting the product into a muffle furnace for roasting at 550 ℃ for 5 hours (the heating rate is 3 ℃ C. min.)-1) Finally, the ordered mesoporous material SBA-15 is prepared.
The second purpose of the invention is to provide the mesoporous carbon material GMC obtained by the preparation method.
The third purpose of the invention is to provide a GMC supported cobalt-based catalyst containing the mesoporous carbon material.
The fourth purpose of the invention is to provide a preparation method of the cobalt-based catalyst loaded by the mesoporous carbon material GMC, which comprises the following steps:
(1) mixing Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol solution;
(2) immersing a mesoporous carbon material GMC into the solution obtained in the step (1), and then evaporating in a rotary evaporator to obtain a mixture;
(3) putting the mixture obtained in the step (2) into an oven for drying; then calcining to obtain the catalyst, which is marked as Co/GMC.
In one embodiment, the Co (NO) of step (1)3)2·6H2O and the mesoporous carbon material in the step (2) in a mass ratio of 1.08: 1.
in one embodiment, the Co (NO) of step (1)3)2·6H2The mass ratio of the O to the absolute ethyl alcohol is 1: 5-50.
In one embodiment, the immersion time of step (2) is 1-2 min.
In one embodiment, the temperature of the rotary evaporator in the step (2) is 35 ℃ and the evaporation time is 5-40 min.
In one embodiment, the drying temperature in step (3) is 50 ℃ for 2-7 h.
In one embodiment, the calcination in step (3) is specifically: in thatN2Calcining at 350 deg.C in atmosphere, and heating at 3 deg.C/min-1The calcination time is 2-10 h.
The fifth purpose of the invention is the application of the mesoporous carbon material GMC in the fields of catalysis, electrochemistry, environment or magnetic catalysis.
A sixth object of the invention is the use of the catalyst of the invention in the industrial production of hydrogen.
The invention has the beneficial effects that:
(1) the mesoporous carbon material GMC supported cobalt-based catalyst is prepared by taking biomass (soybean oil) as a carbon source through a simple one-step solid-liquid ball milling method, and the preparation method is simple and environment-friendly.
(2) The graphitized mesoporous carbon material GMC prepared by the invention has regular and ordered mesoporous structure, relatively large pore volume and specific surface area, and relatively concentrated pore size distribution.
(3) The Co/GMC catalyst has higher graphitization degree, more uniform dispersion of CoO particles, higher CO conversion rate and lower CO2Rate of formation, and C5+The selectivity of the catalyst is better, and the good performance of the Co/GMC used for the Fischer-Tropsch synthesis catalyst is shown.
Drawings
Fig. 1 is an X-ray diffraction pattern of a catalyst in example 1 in which carbon supports were calcined at different temperatures.
Fig. 2 is a raman spectrum of a catalyst of example 1 in which carbon supports were calcined at different temperatures.
FIG. 3 is a TEM photograph of a calcined carbon support catalyst of example 1 at different temperatures, wherein (a) is Co/GMC-700, (b) is Co/GMC-800, and (c) is Co/GMC-900.
Fig. 4 is a nitrogen desorption curve of the catalyst of example 1 in which carbon supports were calcined at different temperatures.
FIG. 5 is a plot of pore size distribution for catalysts of example 1 with different temperature calcined carbon supports
FIG. 6 shows H of the catalyst of example 1 in which carbon carriers were calcined at different temperatures2-a TPR map.
FIG. 7 is a graph of the change in CO conversion during a Fischer-Tropsch synthesis reaction for catalysts of example 1 with different temperature calcined carbon supports.
FIG. 8 is XRD after Fischer-Tropsch synthesis reaction of a catalyst calcined with carbon support at different temperatures of example 1.
FIG. 9 is a transmission electron micrograph (A) of Co/GMC-700, (b) of Co/GMC-800, and (c) of Co/GMC-900 of a calcined carbon support of example 1 taken after a Fischer-Tropsch synthesis reaction.
FIG. 10 is a graph showing the pore size distribution of CMK-3, AC from GMC-800 of example 1 and comparative example 1.
FIG. 11 is a TEM image of GMC-800 of example 1 and CMK-3 of comparative example 1, where (a) is GMC-800 and (b) is CMK-3.
FIG. 12 shows the nitrogen desorption curves of GMC-800 of example 1 and CMK-3 and AC of comparative example 1.
FIG. 13 is a graph showing the isothermal adsorption and desorption curves of nitrogen after loading Co on Co/GMC-800 of example 1, Co/CMK-3 of comparative example 1, and Co/AC carbon support.
FIG. 14 is an XRD pattern of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 1.
FIG. 15 shows Raman spectra of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 1.
FIG. 16 is a TEM photograph of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 1; (a) is Co/GMC-800, (b) is Co/CMK-3, and (c) is Co/AC.
FIG. 17 shows the H values of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 12-a TPR map.
FIG. 18 shows the CO conversion during the Fischer-Tropsch reaction for Co/GMC-800 of example 1, Co/CMK-3 of comparative example 1 and Co/AC.
FIG. 19 is a XRD of a Fischer-Tropsch synthesis reaction of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 1.
FIG. 20 is a TEM image of the Fischer-Tropsch synthesis reaction of Co/GMC-800 of example 1, Co/CMK-3 and Co/AC of comparative example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The X-ray powder diffraction utilizes XRD to effectively determine the structure of an actually measured substance, and different substances have different structural properties, so that the lattice interplanar spacing and the diffraction characteristic peak intensity of the actually measured substance can be combined with standard PDF card for comparison, and the phase composition of the actually measured substance can be further determined, in addition, the diffraction peak intensity and the diffraction peak position of different substances are different, the structural parameter information can be determined by combining with XRD spectrum analysis, CuK α is adopted as a radiation source, the tube pressure is 40KV, the tube current is 200mA, the scanning range (2 theta) is 10-80 degrees, and the scanning step length is 0.02 degree, and the X-ray powder diffraction is obtained by calculation through a Sheble formula:
wherein D is the grain size, K is the Sieve constant, β is the half-peak width of the diffraction peak, lambda is the incident X-ray wavelength, and theta is the diffraction angle.
Transmission electron microscope: the method is characterized in that an electron beam with a short wavelength is used as a light source, then the electron beam is accelerated, gathered and projected on a measured sample, electrons collide with atoms in the sample to change the direction, so that the three-dimensional scattering is generated, and finally the generated influence is amplified and displayed on an imaging device. Preparing a sample: and (3) mixing the ultrasonic sample and absolute ethyl alcohol, then dripping the mixture on a carbon film copper net, and testing after drying.
Nitrogen physical adsorption desorption: the determination of pore size distribution by nitrogen adsorption and desorption is a relatively mature and common method. The method can effectively measure the physical structure characteristics of the catalyst such as specific surface area, pore diameter, pore volume and the like.
Raman spectroscopy: testing an instrument: dilor Labram-1B spectrometer with He-Ne as excitation light source and wavelength of 632.8nm and test range of 1 mm.
H2Temperature programmed reduction (H)2-TPR): placing 0.05g sample in a U-shaped quartz reaction tube, then treating for 2H in He inert atmosphere at 500 ℃, cooling to 60 ℃, and switching to 10% H2Heating the mixed gas of Ar and Ar to 800 ℃ (10 ℃ min)-1Temperature rise), finallyAnd detecting the hydrogen consumption.
Evaluation of catalyst Performance: the Fischer-Tropsch operation flow is as follows: putting a certain amount of catalyst in the middle of a stainless steel reaction tube, opening reducing gas, adjusting a certain pressure for reduction, and adjusting the temperature to 450 ℃ for rise. After the reduction reaction is carried out for 16h, the reducing gas is closed and the reaction furnace is rapidly cooled to room temperature. Gas chromatographs GC-9160 and GC-2060 were opened and the protocol was followed. And opening the synthesis gas and regulating the synthesis gas to a constant flow rate, then heating the reaction furnace to a certain temperature, sampling every 5 hours, reacting for 60 hours, stopping sampling, and closing the synthesis gas and the gas chromatography. The reaction products can be detected analytically by gas chromatography: GC-9160 type gas chromatograph detection: detection of C Using FID1-C30A reaction product; unreacted synthesis gas and short-chain hydrocarbons can be detected by a gas chromatograph model GC-2060: CH detection using FID4、C2H6、C3H8And C4H10(ii) a Detection of H Using TCD2、N2、CO、CH4And CO2。
The specific performance was evaluated as follows:
1) CO conversion (in N) was calculated from the carbon balance2As internal standard):
(2) in the formula, SPrimary N2、SFinal N2And SInitial CO、SFinal CORespectively expressed as initial N corresponding to TCD chromatogram2Finally N2And peak areas of initial CO, final CO.
2)CH4Amount of product:
n after separation according to TDX-01 column2And CH4The peak area of (A) can be determined to obtain CH formed in the reaction4The amount of substance(s) of (c).
In the formula (3), SCH4、SN2And fCH4、fN2Respectively expressed as corresponding CH in TCD chromatogram4And N2Area peaks and their internal standard factors.
3)CnSelectivity of the product:
the amount of each hydrocarbon product substance (in terms of the amount of carbon atom-containing substance) in the reaction product was determined from the proportional relationship of all the products detected by gas chromatography. Then with CH4And as a second internal standard, the peak area of each hydrocarbon after FID separation is used for respectively obtaining the amount of each component substance in the product:
the hydrocarbon product selectivity is calculated from equation (5)
Example 1
A preparation method of a cobalt-based catalyst loaded by a mesoporous carbon material GMC comprises the following steps:
(1) preparation of ordered mesoporous carbon material (GMC):
mixing SBA-15 and soybean oil (mass ratio of 1:2) by solid-liquid ball milling template method at 400rpm min-1Ball milling for 5h at rotating speed, mixing, dividing the mixture into three parts, sequentially transferring into a quartz tube furnace, and performing ball milling in N2At 4 ℃ per minute under protection-1Respectively heating to 700 deg.C, 800 deg.C and 900 deg.C, and carbonizing for 5h to obtain three calcined materials with different temperatures. And etching with NaOH solution (concentration 2mol/L) for 3 times, wherein the etching time is 24h each time, so as to remove the hard template agent SBA-15, and finally obtaining the porous materials calcined at different temperatures, which are respectively marked as GMC-700, GMC-800 and GMC-900.
(2) Preparing GMC-700, GMC-800 and GMC-900 catalysts by an impregnation method:
0.8719g of Co (NO) was taken3)2·6H2O was dissolved in an excess of the anhydrous ethanol solution, and then 0.8g of a porous carbon material (GMC-700, GMC-800. GMC-900) was immersed in an excess of an ethanol solution of cobalt nitrate, followed by slow evaporation at 35 ℃ in a rotary evaporator, and the sample was then dried in an oven at 50 ℃. Finally, the catalyst is placed in N2Calcining at 350 deg.C (at 3 deg.C. min) under atmosphere-1Raising the temperature) to finally obtain three catalysts, namely Co/GMC-700, Co/GMC-800 and Co/GMC-900 respectively. Comparative example 1: the carbon material in example 1 was replaced with mesoporous carbon CMK-3, activated carbon AC
(1) And (3) synthesizing and preparing ordered mesoporous carbon CMK-3:
and (3) fully and uniformly mixing 9g of SBA-15 with 45mL of sucrose concentrated sulfuric acid mixed solution (the mass ratio is 9:1), and then respectively baking at 110 ℃ and 160 ℃ for 6 h. After drying, mixing the obtained solid with 45mL of sucrose concentrated sulfuric acid mixed solution (the mass ratio is 9:1) again, and then drying at 110 ℃ and 160 ℃ for 6 hours respectively. Then N2At 4 ℃ per minute under protection-1And (3) heating to 900 ℃ for carbonization for 5h, then fully treating the carbonized sample with 2mol/L NaOH solution, carrying out suction filtration, washing with deionized water for 2-3 times, and finally drying at 100 ℃.
(2) Preparation of the catalyst:
0.8719g of Co (NO) was taken3)2·6H2O was dissolved in an excess of an absolute ethanol solution, and then 0.8g of a carbon material (mesoporous carbon CMK-3, activated carbon AC) was immersed in an excess of an ethanol solution of cobalt nitrate, followed by slow evaporation at 35 ℃ in a rotary evaporator, and then the sample was put into an oven to be dried at 50 ℃. Finally, the catalyst is placed in N2Calcining at 350 deg.C (at 3 deg.C. min) under atmosphere-1And (4) raising the temperature), and finally obtaining two catalysts, namely Co/CMK-3 and Co/AC respectively.
The catalysts of example 1 and comparative example 1 were subjected to performance tests, and the specific test results were as follows:
fig. 1 is an X-ray diffraction pattern of a catalyst in example 1 in which carbon supports were calcined at different temperatures. As can be seen from fig. 1: the diffraction peak at 26.6 degrees corresponds to the characteristic diffraction peak of graphitized carbon, and compared with the XRD diffraction peak of a cobalt-based catalyst loaded after calcining a carbon carrier at different temperatures, the mesoporous carbon material with high calcining temperature has high graphitization degree. And diffraction peaks at 36.4 degrees, 42.3 degrees, 61.6 degrees, 73.9 degrees and 77.8 degrees belong to characteristic diffraction peaks of different crystal planes of CoO (JCPDS 43-1004) on the surface of the catalyst. Only CoO is present on the surface of the support and no other cobalt oxides are present. In addition, the CoO peaks formed on the cobalt-based catalyst of mesoporous carbon calcined at different temperatures have different intensities, which shows that the CoO particles have different sizes, and the influence of the structure of the carbon carrier, such as graphitization degree, porosity and the like, on the particle size is shown. The average particle sizes of CoO in the carbon support-supported cobalt-based catalyst after calcination at temperatures of 700, 800, and 900 ℃ were calculated to be 10.1, 11.6, and 8.1nm, respectively, by the scherrer equation.
Fig. 2 is a raman spectrum of a catalyst of example 1 in which carbon supports were calcined at different temperatures. As seen from the figure: 2 peaks of scattered intensity, the former being caused by defects in the single crystal graphite and being called D peaks, the latter being caused by sp carbon atoms2The hybrid in-plane stretching vibration causes what is called the G peak. In general, the ratio of the areas of the D peak and the G peak determines the degree of graphitization of the carbon material, ID/IGThe smaller the ratio (area ratio of two peaks) is, the higher the graphitization degree of the carbon material produced is. I of Co/GMC-700, Co/GMC-800, Co/GMC-900D/IGThe ratios of (A) to (B) are 1.879, 1.744 and 1.550, respectively, and thus the Co/GMC-900 catalyst has a higher degree of graphitization when calcined at 900 ℃. In addition, the increase in the carrier calcination temperature shifts the peak in the short-wave number direction, i.e., red shift occurs, which is caused by the graphitization defect.
FIG. 3 is a TEM photograph of a calcined carbon support catalyst of example 1 at different temperatures, wherein (a) is Co/GMC-700, (b) is Co/GMC-800, and (c) is Co/GMC-900. As can be seen from the figure: cobalt metal particles are uniformly dispersed on the surface of the mesoporous carbon carrier and the inner surface of the pore channel, and the mesoporous structure of carbon is damaged along with the increase of the calcination temperature of the carbon material. In addition, the particle size distribution diagram obtained by TEM shows that the particle sizes of CoO in Co/GMC-700, Co/GMC-800 and Co/GMC-900 are respectively 10.5-15.5 nm, 9-12 nm and 7-9 nm, which are basically consistent with the particle size obtained by XRD.
Fig. 4 is a nitrogen desorption curve of the catalyst of example 1 in which carbon supports were calcined at different temperatures. As can be seen from the figure: the three different catalysts are at relative pressure P/P0The absorption and desorption curves belong to class IV isothermal adsorption curves, the carbon carrier has a mesoporous structure, and the hysteresis loop of the carbon carrier with higher calcination temperature is larger, which is probably caused by the larger pore volume. At the onset point B of the hysteresis loop, capillary condensation begins to appear in the smallest pores. With relative pressure P/P0Gradually rising, capillary condensation gradually appears in the middle hole until the pressure is saturated, the whole system is filled with the condensation liquid, and a larger hysteresis loop appears.
Fig. 5 is a plot of the pore size distribution of catalysts of example 1 with different temperature calcined carbon supports. As can be seen from the figure: the pore diameters of the three catalysts, Co/GMC-700, Co/GMC-800 and Co/GMC-900, were substantially concentrated at 3.9 nm.
Table 1 shows the specific surface areas, pore diameters and average pore volumes of Co/GMC-700, Co/GMC-800 and Co/GMC-900 in example 1. As can be seen from the table, the specific surface areas of the catalysts Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 207m, respectively2.g-1、246m2.g-1、306m2.g-1(ii) a The average pore volumes of the catalysts Co/GMC, Co/GMC-800 and Co/GMC-900 were 0.12cm respectively3.g-1、0.22cm3.g-1、0.26cm3.g-1. From the above, as the calcination temperature of the carbon support increases, the specific surface area and the total volume of the catalyst increase.
TABLE 1 specific surface area, pore size and mean pore volume data for Co/GMC-700, Co/GMC-800 and Co/GMC-900 of example 1
| Sample (I) | Specific surface area (m)2.g-1) | Pore size (nm) | Average pore diameter (cm)3.g-1) |
| Co/GMC-700 | 207 | 2.29 | 0.12 |
| Co/GMC-800 | 246 | 3.62 | 0.22 |
| Co/GMC-900 | 306 | 3.51 | 0.26 |
FIG. 6 shows H of the catalyst of example 1 in which carbon carriers were calcined at different temperatures2-a TPR map. As can be seen from the figure: all catalysts exhibited three hydrogen reduction peaks, with the first reduction peak from left to right representing Co3O4The hydrogen reduction peak → CoO, while the second represents the hydrogen reduction peak CoO → Co, and the third represents the vaporization peak of the carbon carrier. In addition, no reduction peak is generated above 700 ℃, which shows that no compound which is difficult to reduce is generated on the surface of the catalyst. Co-based catalyst loaded by carbon carrier with higher calcination temperature3O4The reduction temperature of the active phase → CoO → Co is also higher, indicating that the carbon carrier calcined at higher temperature is more beneficial to increase the enhancement of the interaction force between the mesoporous carbon carrier and the cobalt. BET analysis by combining TEM with nitrogen physical adsorption shows that: the collapse of the mesoporous structure of the mesoporous carbon material introduces more physical defects, improves the dispersing capacity of cobalt on the mesoporous carbon carrier, and the reduction of the particle size of the cobalt enhances the interaction force between the cobalt and the carrier, thereby improving the stability of the catalyst.
FIG. 7 is a graph of the change in CO conversion during a Fischer-Tropsch synthesis reaction for catalysts of example 1 with different temperature calcined carbon supports. As can be seen from the figure: the carbon carrier calcined at higher temperature has higher CO conversion rate, and combined with TEM and nitrogen adsorption and desorption BET analysis, the CO conversion rate of the Co/GMC-800 catalyst calcined at 800 ℃ is relatively lower probably because more physical defects are generated on the surface of the mesoporous carbon carrier due to the increase of temperature, mesopores are fully opened, the surface area of the carbon carrier is increased, and the CO conversion rate of the Co/GMC-800 catalyst calcined at 800 ℃ is relatively lower because the specific surface area of Co/GMC-800 is slightly increased compared with that of Co/GMC-700 and the granularity of Co/GMC-800 is larger. After the performance evaluation of the Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts for 60 hours, the CO conversion rates are respectively reduced from 45%, 37% and 55% to 35%, 26% and 42%.
Table 2 shows the Fischer-Tropsch catalytic reaction performance of the Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts of example 1, as shown in the table: c of Co/GMC-9005+Has higher selectivity, which can promote the electron transfer capacity between the metal cobalt and the CO due to the stronger graphitization degree and the graphite defect, further activates CO molecules, increases the CO molecules adsorbed on the surface of the catalyst, and is beneficial to forming C5+Mixtures of the above.
TABLE 2 Fischer-Tropsch Synthesis catalyst Performance of Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts from example 1
aThe reaction conditions are that T is 270 ℃, P is 2MPa, and H2/CO＝2,GHSV＝3.6L·h-1g-1
bThe selectivity of hydrocarbons is standardized, except for carbon dioxide.
cC＝/CnIs C2-4The molar ratio of olefin to paraffin wax.
FIG. 8 is XRD after Fischer-Tropsch synthesis reaction of a catalyst calcined with carbon support at different temperatures of example 1. As can be seen from the figure: the 2 theta values of three obvious diffraction peaks of Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 42.5 degrees,45.7 DEG and 68.3 DEG, corresponding to Co2Diffraction characteristic peak of C (JCPDS 72-1369), and another diffraction peak Co3C (JCPDS89-2866) corresponding to 60 degrees, 60 degrees and 75 degrees of Co/GMC-700, 60 degrees, 75 degrees and 83 degrees of Co/GMC-800, respectively. In addition, the catalysts Co/GMC-700, Co/GMC-800 and Co/GMC-900 after the reaction all have graphitization peaks when the 2 theta is 26.1 degrees, but the highest value is Co/GMC-900.
FIG. 9 is a transmission electron micrograph (A) of Co/GMC-700, (b) of Co/GMC-800, and (c) of Co/GMC-900 of a calcined carbon support of example 1 taken after a Fischer-Tropsch synthesis reaction. As can be seen from the figure: along with the change of reaction time, the particle size of CoO particles is continuously increased to generate an agglomeration phenomenon; the particle diameters of CoO particles are respectively 10.5-14 nm, 12.5-17.5 nm and 10-14 nm.
FIG. 10 is a graph showing the pore size distribution of CMK-3, AC from GMC-800 of example 1 and comparative example 1. As can be seen from the figure: the pore size distribution of GMC-800, CMK-3 and AC is mainly concentrated in 3.6nm, 3.9nm and 3.9nm, which shows that the carbon material prepared by using SBA-15 as a hard template agent has an ordered mesoporous structure.
FIG. 11 is a TEM image of GMC-800 of example 1 and CMK-3 of comparative example 1, where (a) is GMC-800 and (b) is CMK-3. As can be seen from the figure: the prepared GMC-800 and CMK-3 have ordered structures.
FIG. 12 shows the nitrogen desorption curves of GMC-800 of example 1 and CMK-3 and AC of comparative example 1. As seen from the figure: in the low region P/P0(0-0.4), a strong absorption peak is present, which is characteristic of micropores; at a relative pressure P/P0When the molecular weight is 0.4-1, GMC-800 and CMK-3 both have hysteresis loops, which shows that the absorption and desorption curves of the two are typical IV-type curves and have typical mesoporous structures. And the adsorption and desorption curve of AC is I-type isotherm and has a microporous structure. As shown, N of the catalyst2The adsorption and desorption isotherms are similar to their corresponding adsorption and desorption isotherms of the carrier, which indicates that the structural performance of the catalyst carrier changes little during the preparation process.
FIG. 13 shows the isothermal curves of nitrogen physisorption desorption after loading Co on Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC carbon carriers of comparative example 1 with Co. As seen from the figure:the specific surface area, pore size and pore volume of CMK-3 were all the largest among the three carbon support materials, 939m each2.g-1、1.31cm3.g-1And 5.57 nm. The specific surface areas of AC and CMK-3 are both higher than GMC-800. The average pore size of CMK-3 was the largest (5.57nm), AC the smallest (2.25nm) and GMC-800 centered (5.57nm) for the control support. In addition, after 15 wt.% of cobalt element was supported on the corresponding carbon support, the specific surface area and pore volume of the support were significantly reduced. Possibly due to the filling of the pores on the surface of the support with oxidic particles of cobalt.
Table 3 shows the physicochemical properties of CMK-3 and AC-loaded cobalt in the carbon material GMC-800 of example 1 and comparative example 1. As can be seen from the table: the specific surface area, pore size and pore volume of CMK-3 were all the largest among the three carbon support materials, 939m each2.g-1、1.31cm3.g-1And 5.57 nm. The specific surface areas of AC and CMK-3 are both higher than GMC-800. The average pore size of CMK-3 was the largest (5.57nm), AC the smallest (2.25nm) and GMC-800 centered (5.57nm) for the control support. In addition, after 15 wt.% of cobalt element was supported on the corresponding carbon support, the specific surface area and pore volume of the support were significantly reduced.
Table 3 shows the physicochemical properties of the carbon material GMC-800 of example 1 and CMK-3 and before and after AC loading with cobalt of comparative example 1
| Sample (I) | Specific surface area (m)2.g-1) | Pore size (nm) | Average pore diameter (cm)3.g-1) |
| GMC | 442 | 5.24 | 0.58 |
| CMK-3 | 939 | 5.57 | 1.31 |
| AC | 657 | 2.25 | 0.37 |
| Co/GMC-800 | 246 | 3.62 | 0.22 |
| Co/CMK-3 | 709 | 4.30 | 0.76 |
| Co/AC | 492 | 2.44 | 0.30 |
FIG. 14 is an XRD pattern of Co/GMC-800 of example 1 and Co/CMK-3, Co/AC of comparative example 1. As seen from the figure: as the small-angle X-ray diffraction pattern of the mesoporous material mainly has diffraction peaks at 1-2 positions, the prepared catalysts Co/GMC-800 and Co/CMK-3 have diffraction peaks at 1.039 positions, which shows that the catalysts have mesoporous structures. In addition, it can be seen from the figure that: the diffraction peak at 26.6 degrees 2 theta corresponds to the characteristic diffraction peak of graphitized carbon, and shows that the graphitization degree of the porous carbon material GMC is much higher than that of CMK-3 and AC. And diffraction peaks at 36.4 °, 42.3 °, 61.6 °, 73.9 °, and 77.8 ° indicate that the cobalt nanoparticles in the catalyst are mainly present in the form of CoO (JCPDS 43-1004). Comparing the CoO characteristic diffraction peak intensities of different catalysts in the figure, the peak intensity of the CoO of the catalyst Co/AC is found to be stronger than that of the catalysts Co/GMC-800 and Co/CMK-3, which shows that the CoO particles on the catalyst Co/AC are larger. The average particle sizes of Co/GMC-800, Co/CMK-3 and Co/AC catalyst CoO are respectively 11.6nm, 6.9nm and 19.2nm calculated by the Shele equation.
FIG. 15 shows Raman spectra of Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC of comparative example 1. As seen from the figure: the Raman spectrum has 2 scattering intensity peaks, the former is caused by single crystal graphite defects and is called D peak, the latter is caused by carbon atom sp2The hybrid in-plane stretching vibration causes what is called the G peak. In general, the ratio of the areas of the D peak and the G peak determines the degree of graphitization of the carbon material, ID/IGThe smaller the ratio (area ratio of two peaks) is, the higher the graphitization degree of the carbon material produced is. As can be seen from FIG. 3.6, I of Co/GMC-800, Co/CMK-3, Co/ACD/IGThe ratios of (A) to (B) are 1.94, 1.98 and 2.65 respectively, which indicates that the graphitization degree of Co/GMC-800 and Co/CMK-3 is relatively high.
FIG. 16 is a TEM photograph of Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC of comparative example 1; (a) is Co/GMC-800, (b) is Co/CMK-3, and (c) is Co/AC. As seen from the figure: the catalysts Co/GMC-800 and Co/CMK-3 have mesoporous structures. CoO particles are uniformly dispersed on the mesoporous carbon material GMC, and the structure of the CoO particles is regular; after the mesoporous carbon material CMK-3 is loaded with cobalt, the ordered mesoporous structure is partially collapsed, but CoO nanoparticles can be uniformly dispersed on the CMK-3 carrier. Whereas for Co/AC the CoO is relatively concentrated in dispersion. In addition, the particle size distribution diagram obtained by TEM shows that the particle sizes of CoO in Co/GMC-800, Co/CMK-3 and Co/AC are respectively 9-12 nm, 6.5-8 nm and 12-17.5 nm.
FIG. 17 shows the H values of Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC of comparative example 12-a TPR map. As seen from the figure: all catalysts exhibited three hydrogen reduction peaks, with the first reduction peak from left to right representing Co3O4The hydrogen reduction peak → CoO, while the second reduction peak represents the hydrogen reduction peak CoO → Co, and the third reduction peak represents the vaporization peak of the carbon carrier. No reduction peak appears above 700 ℃, indicating that no compound difficult to reduce is generated on the surface of the catalyst, which also indicates that the interaction force between the cobalt oxide and the carbon carrier is larger than that of the oxide carrier (for example: SiO)2And Al2O3) The interaction with the cobalt catalyst is much weaker.
FIG. 18 shows the CO conversion during the Fischer-Tropsch reaction for Co/GMC-800 of example 1 and Co/CMK-3, Co/AC of comparative example 1. As seen from the figure: the stability of the three catalysts is not uniform due to the influence of the structural properties of the carrier. The catalytic activity of the catalyst Co/CMK-3 is stable, after the catalytic reaction is carried out for 60 hours, the CO conversion rate is reduced by 15% from 21%, the CO conversion rate of Co/GMC is reduced by 26% from 37%, and the CO conversion rate of Co/AC is reduced by 9% from 19%.
Table 4 shows the Fischer-Tropsch catalytic performance of the Co/GMC-800 of example 1 and the Co/CMK-3, Co/AC catalysts of comparative example 1. As can be seen from the table: Co/GMC-800 has a higher Conv.CO(29.4%), which is probably due to the higher graphitization degree of GMC-800, the electron transfer between cobalt and CO is facilitated, and the CO activation is further promoted. While the Co/CMK-3 catalyst has larger specific surface area and pore volume, but Conv.COOnly 18.05 percent, probably caused by the amorphous performance of CMK-3 after loading cobalt, poor graphitized structure and the damage of partially ordered structure in the preparation process. In addition, it can be seen from the table that: high C5+Selectivity is often accompanied by low CH4And C2-C4Selectivity, catalyst Co/GMC-800 can obtain more C than catalysts Co/CMK-3 and Co/AC5+Hydrocarbon products and lower methane and C2-C4. The reason is that the graphitization degree of the catalyst is stronger, so that the electron transfer capability between the metal cobalt and CO is promoted, and then CO molecules are activated, so that the CO molecules adsorbed on the surface of the catalyst are increased, and the formation of C is facilitated5+Mixtures of the above.
TABLE 4 Fischer-Tropsch Synthesis catalyst Performance of Co/GMC-800 of example 1 and Co/CMK-3, Co/AC catalysts of comparative example 1
aThe reaction conditions are that T is 270 ℃, P is 2MPa, and H2/CO＝2,GHSV＝3.6L·h-1g-1
bThe selectivity of hydrocarbons is standardized, except for carbon dioxide.
cC＝/CnIs C2-4The molar ratio of olefin to paraffin wax.
FIG. 19 is an XRD of the Fischer-Tropsch synthesis reaction of Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC of comparative example 1. As seen from the figure: the 2 theta values of three distinct diffraction peaks of Co/GMC and Co/CMK-3 are 42.5 deg., 45.7 deg. and 68.3 deg., corresponding to Co2The diffraction characteristic peak of C (JCPDS 72-1369), and the other two diffraction peaks correspond to Co3C (JCPDS89-2866) with 2 theta values of 60 DEG and 75 deg. This illustrates the appearance of new species in the catalyst after the reaction, which is also a major cause of carbon monoxide decline over time during the reaction. In addition, the graphitization diffraction peaks of the catalysts Co/GMC and Co/CMK-3 after the reaction at 26.1 degrees of 2 theta are obviously enhanced.
FIG. 20 is a TEM photograph of Co/GMC-800 of example 1 and Co/CMK-3 and Co/AC of comparative example 1 after Fischer-Tropsch synthesis reaction. As seen from the figure: with the change of reaction time, the particle size of CoO particles is continuously increased, and the agglomeration phenomenon occurs. The particle size distribution diagram obtained by TEM shows that the particle sizes of CoO in Co/GMC-800, Co/CMK-3 and Co/AC are respectively 12.5-17.5 nm, 12-17 nm and 15-25 nm. The reason why the catalyst CO conversion rate decreased faster after nitrogen doping was also confirmed.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a mesoporous carbon material is characterized by comprising the following steps:
s1: uniformly mixing SBA-15 and soybean oil by adopting a solid-liquid ball milling template method;
s2: transferring the mixture of S1 into a quartz tube furnace, and heating to 700-900 ℃ for carbonization;
s3: and etching the mixture of S2 with NaOH solution to obtain the mesoporous carbon material.
2. The method of claim 1, wherein the mass ratio of SBA-15 to soybean oil mixture of S1 is 1: 2.
3. The preparation method according to claim 1, wherein the carbonization process of S2 is specifically: in N2Under protection, the heating rate is 4 ℃ min-1The carbonization time is 5 h.
4. The mesoporous carbon material obtained by the preparation method of claim 1.
5. A cobalt-based catalyst comprising the mesoporous carbon material of claim 1 supported thereon.
6. The method for preparing the catalyst according to claim 5, comprising the steps of:
(1) mixing Co (NO)3)2·6H2Dissolving O in absolute ethyl alcohol solution;
(2) immersing a mesoporous carbon material into the solution obtained in the step (1), and then evaporating in a rotary evaporator to obtain a mixture;
(3) putting the mixture obtained in the step (2) into an oven for drying; then calcining to obtain the catalyst.
7. The method according to claim 6, wherein the Co (NO) of step (1)3)2·6H2The mass ratio of the O to the absolute ethyl alcohol is 1: 5-50.
8. The preparation method according to claim 6, wherein the calcination in step (3) is specifically: in N2Calcining at 350 deg.C in atmosphere, and heating at 3 deg.C/min-1The calcination time is 2-10 h.
9. The mesoporous carbon material of claim 4, for use in the fields of catalysis, electrochemistry, environment or magnetic catalysis.
10. The use of a cobalt-based catalyst supported on a mesoporous carbon material as claimed in claim 5 in industrial hydrogen production.
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| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
| CN113231641A (en) * | 2021-05-08 | 2021-08-10 | 中国科学技术大学 | Carbon black loaded highly-ordered PtCo intermetallic compound and synthesis method and application thereof |
| CN113318737A (en) * | 2021-06-29 | 2021-08-31 | 大连大学 | Copper/porous carbon catalyst and preparation method and application thereof |
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| CN115337930B (en) * | 2022-08-19 | 2024-03-15 | 常州大学 | Preparation method of graphitized carbon modified shell-core Co-based catalyst and application of graphitized carbon modified shell-core Co-based catalyst in carbon monoxide hydrogenation catalysis |
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| KR101473319B1 (en) * | 2007-10-16 | 2014-12-16 | 삼성에스디아이 주식회사 | Hierarchical mesoporous carbon, manufacturing method thereof, and fuel cell using the same |
| CN101822987B (en) * | 2010-04-22 | 2012-07-04 | 浙江大学 | Method for modifying active carbon for catalytically decomposing hydrogen iodide by adding active metal |
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| EP3251747A1 (en) * | 2016-05-31 | 2017-12-06 | Studiengesellschaft Kohle mbH | Process for preparing mesoporous carbon loaded with catalytically active metal and/or metal oxide nanoparticles for the selective transfer hydrogenation of alpha-beta-unsaturated aldehydes to unsaturated alcohols |
| CN107519875B (en) * | 2017-09-05 | 2019-12-03 | 济南大学 | A kind of preparation method and application of carbon substrate Supported Co oxidate nano composite material |
| CN110961137A (en) * | 2019-12-20 | 2020-04-07 | 常州工学院 | Nitrogen-doped graphitized porous carbon-loaded cobalt-based catalyst and preparation method thereof |
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| WO2021121088A1 (en) * | 2019-12-20 | 2021-06-24 | 常州工学院 | Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor |
| CN113231641A (en) * | 2021-05-08 | 2021-08-10 | 中国科学技术大学 | Carbon black loaded highly-ordered PtCo intermetallic compound and synthesis method and application thereof |
| CN113231641B (en) * | 2021-05-08 | 2022-07-15 | 中国科学技术大学 | Carbon black loaded highly-ordered PtCo intermetallic compound and synthesis method and application thereof |
| CN113318737A (en) * | 2021-06-29 | 2021-08-31 | 大连大学 | Copper/porous carbon catalyst and preparation method and application thereof |
| CN113457657A (en) * | 2021-06-29 | 2021-10-01 | 大连大学 | Carbon-based methanol hydrogen production catalyst and preparation method and application thereof |
| WO2023273670A1 (en) * | 2021-06-29 | 2023-01-05 | 大连大学 | Carbon-based methanol hydrogen-production catalyst, preparation method therefor, and application thereof |
| CN114797847A (en) * | 2022-05-17 | 2022-07-29 | 中山大学 | Metal-doped mesoporous carbon-based catalyst and preparation method and application thereof |
| CN114797847B (en) * | 2022-05-17 | 2024-04-23 | 中山大学 | Metal doped mesoporous carbon-based catalyst and preparation method and application thereof |
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