WO2021121088A1 - Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor - Google Patents

Mesoporous carbon material loaded cobalt-based catalyst and preparation method therefor Download PDF

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WO2021121088A1
WO2021121088A1 PCT/CN2020/134712 CN2020134712W WO2021121088A1 WO 2021121088 A1 WO2021121088 A1 WO 2021121088A1 CN 2020134712 W CN2020134712 W CN 2020134712W WO 2021121088 A1 WO2021121088 A1 WO 2021121088A1
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gmc
carbon material
catalyst
preparation
mesoporous carbon
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French (fr)
Chinese (zh)
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柏寄荣
王志磊
许�鹏
邓瑶瑶
周全法
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常州工学院
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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
    • B01J35/393—
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a cobalt-based catalyst supported by a mesoporous carbon material and a preparation method thereof, and belongs to the technical field of metal catalysts.
  • biomass is one of the core topics. It has the advantages of wide sources, wide variety, and great development potential. People use biomass to convert it into fuel, electricity, etc., not only to solve the energy problem, but also to reuse some waste biomass.
  • Porous carbon materials not only have the advantages of carbon materials such as acid and alkali resistance, high temperature resistance, stable chemical properties, and low cost, but also have excellent properties such as regular pore structure, large specific surface area, and adjustable pore size.
  • porous carbon materials have a higher specific surface area, pore volume, and large pore diameter.
  • this porous carbon material also has certain limitations in practical applications, such as: the prepared material replicates the template The structure cannot be changed arbitrarily.
  • the choice of carrier is closely related to the catalytic performance of the catalyst. If the interaction between the support and the metal is too strong, it will affect the dispersibility of the metal and is not conducive to the reduction of the metal; on the contrary, it will reduce the stability of the metal.
  • the active phase of the cobalt-based catalyst 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.
  • many research works have used carriers with high specific surface and well-developed pores, such as TiO 2 , Al 2 O 3 , and SiO 2 to support active components.
  • carriers with high specific surface and well-developed pores such as TiO 2 , Al 2 O 3 , and SiO 2 to support active components.
  • this type of carrier and active components are prone to form difficult-to-reducible species, which makes it difficult to obtain a unified active phase with high dispersion and high reduction on the surface of the catalyst.
  • the present invention provides a cobalt-based catalyst supported by mesoporous carbon materials and a preparation method thereof.
  • the catalyst of the present invention has a higher CO conversion rate and better catalytic reaction performance; the C 5+ selectivity is significantly improved.
  • the first object of the present invention is to provide a method for preparing mesoporous carbon material, the specific steps are:
  • S2 Transfer the mixture of S1 into a quartz tube furnace and heat up to 700-900°C for carbonization;
  • S3 The mixture of S2 is etched with NaOH solution to obtain the mesoporous carbon material, which is marked as mesoporous carbon material GMC.
  • the mass ratio of SBA-15 and soybean oil mixture described in S1 is 1:2.
  • the mixing method described in S1 is: ball milling with a ball mill at a speed of 400 rpm ⁇ min -1 for 5 hours.
  • the carbonization process described in S2 is specifically: under the protection of N 2 , the heating rate is 4° C. ⁇ min -1 , and the carbonization time is 5 h.
  • the concentration of the NaOH solution described in S3 is 2 mol/L.
  • the number of etchings described in S3 is 3 times, and each etching time is 24 hours.
  • the preparation method of SBA-15 are as follows: First, 3.0g of surfactant P123 3.0g of glycerin and after mixing, was added to a dilute hydrochloric acid solution 115.0mL (1.5mol.L - 1 ) Then stir in a 37°C water bath for transparency. After 3 hours, stir vigorously and add 6.45g diethyl orthosilicate (TEOS) dropwise.
  • TEOS diethyl orthosilicate
  • the second object of the present invention is to provide a mesoporous carbon material GMC obtained by the preparation method of the present invention.
  • the third object of the present invention is to provide a cobalt-based catalyst containing the mesoporous carbon material GMC supported by the present invention.
  • the fourth object of the present invention is to provide a method for preparing the mesoporous carbon material GMC-supported cobalt-based catalyst of the present invention, which includes the following steps:
  • step (2) Immerse the mesoporous carbon material GMC in the solution of step (1), and then evaporate in a rotary evaporator to obtain a mixture;
  • step (3) Put the mixture of step (2) into an oven to dry; then calcinate, and then the catalyst can be obtained.
  • the mass ratio of the Co(NO 3 ) 2 ⁇ 6H 2 O described in step (1) and the mesoporous carbon material described in step (2) is 1.08:1.
  • the mass ratio of Co(NO 3 ) 2 ⁇ 6H 2 O and absolute ethanol mentioned in step (1) is 1:5-50.
  • the immersion time in step (2) is 1-2 min.
  • the temperature of the rotary evaporator described in step (2) is 35° C., and the evaporation time is 5-40 min.
  • the drying temperature in step (3) is 50°C for 2-7 hours.
  • the calcination described in step (3) is specifically: calcination at 350° C. in an N 2 atmosphere, a heating rate of 3° C. ⁇ min -1 , and a calcination time of 2-10 h.
  • the fifth objective of the present invention is the application of the mesoporous carbon material GMC of the present invention in the fields of catalysis, electrochemistry, environment or magnetocatalysis.
  • the sixth object of the present invention is the application of the catalyst of the present invention in industrial hydrogen production.
  • biomass (soybean oil) is used as a carbon source to prepare a mesoporous carbon material GMC-supported cobalt-based catalyst through a simple one-step solid-liquid ball milling method, and the preparation method is simple and environmentally friendly.
  • the graphitized mesoporous carbon material GMC prepared by the present invention has a regular and orderly mesoporous structure, relatively large pore volume and specific surface area, and relatively concentrated pore size distribution.
  • the Co/GMC catalyst of the present invention has a higher degree of graphitization, a more uniform dispersion of CoO particles, a higher CO conversion rate and a lower CO 2 generation rate, and the C 5+ selectivity is better, showing Co/GMC is used for Fischer-Tropsch synthesis catalyst with good performance.
  • FIG. 1 is the X-ray diffraction spectrum of the catalyst calcined with carbon support at different temperatures in Example 1.
  • FIG. 1 is the X-ray diffraction spectrum of the catalyst calcined with carbon support at different temperatures in Example 1.
  • Fig. 2 shows the Raman spectra of the catalysts calcined with carbon supports at different temperatures in Example 1.
  • Fig. 3 is a transmission electron microscope photograph of the catalyst calcined on a carbon support at different temperatures in Example 1, (a) Co/GMC-700, (b) Co/GMC-800, and (c) Co/GMC-900.
  • FIG. 4 shows the nitrogen adsorption and desorption curves of the catalyst calcined with carbon support at different temperatures in Example 1.
  • FIG. 4 shows the nitrogen adsorption and desorption curves of the catalyst calcined with carbon support at different temperatures in Example 1.
  • Figure 5 is the pore size distribution curve of the catalyst calcined with carbon support at different temperatures in Example 1
  • Fig. 6 shows the H 2 -TPR patterns of the catalyst calcined with a carbon support at different temperatures in Example 1.
  • Fig. 7 shows the change in CO conversion rate of the catalyst calcined with carbon support at different temperatures in Example 1 during the Fischer-Tropsch synthesis reaction.
  • FIG. 8 shows the XRD after the Fischer-Tropsch synthesis reaction of the catalyst calcined with carbon support at different temperatures in Example 1.
  • Fig. 9 is a transmission electron microscope photograph of the catalyst Fischer-Tropsch synthesis reaction of the carbon support calcined at different temperatures in Example 1, (a) is Co/GMC-700, (b) is Co/GMC-800, (c) Co/ GMC-900.
  • FIG. 10 is a pore size distribution diagram of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1.
  • FIG. 10 is a pore size distribution diagram of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1.
  • Fig. 11 is a TEM image of GMC-800 of Example 1 and CMK-3 of Comparative Example 1, (a) is GMC-800, and (b) is CMK-3.
  • Figure 12 shows the nitrogen physical adsorption and desorption curves of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1.
  • Fig. 13 shows the physical adsorption and desorption isotherms of nitrogen after Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC carbon supports of Comparative Example 1 loaded with cobalt.
  • FIG. 14 is an XRD pattern of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • FIG. 14 is an XRD pattern of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • Figure 15 shows the Raman spectra of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • Figure 16 is a transmission electron micrograph 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. (c) is Co/AC.
  • FIG. 17 shows the H 2 -TPR patterns of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • Figure 18 shows the changes in the CO conversion rate of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 during the Fischer-Tropsch synthesis reaction.
  • FIG. 19 shows the XRD after the Fischer-Tropsch synthesis reaction of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • X-ray powder diffraction can effectively determine the structure of the measured substance. Because different materials have different structural properties, the lattice spacing and diffraction characteristic peak intensity of the measured material can be compared with the standard PDF card to determine the phase composition of the measured material. In addition, because different substances have different diffraction peak intensities and different positions of diffraction peaks, it can be combined with XRD pattern analysis to determine their structural parameter information. Using CuK ⁇ as the radiation source, the tube pressure is 40KV, the tube current is 200mA, the scanning range (2 ⁇ ) is 10° ⁇ 80°, and the scanning step length is 0.02°. Calculated by the Xie Le formula:
  • D is the grain size
  • K is the Scherrer constant
  • ⁇ is the half-width of the diffraction peak
  • ⁇ is the incident X-ray wavelength
  • ⁇ is the diffraction angle
  • Transmission electron microscope Use electron beam with a short wavelength as the light source, and then accelerate it to gather and project it on the measured sample. The electrons collide with the atoms in the sample to change the direction, thereby generating three-dimensional scattering, and finally magnifying the impact. On the imaging device. Sample preparation: ultrasonic sample + absolute ethanol mixture, then drip it on the carbon film copper net, and test after drying.
  • Nitrogen physical adsorption and desorption Nitrogen adsorption and desorption is a relatively mature and common method to determine the pore size distribution. It can effectively measure the physical structure characteristics of the catalyst such as specific surface area, pore size and pore volume.
  • Raman spectroscopy Test instrument: Dilor Labram-1B spectrometer, with He-Ne as the excitation light source, its wavelength is 632.8nm, and the test range is 1mm.
  • H 2 temperature-programmed reduction Place 0.05g sample in a U-shaped quartz reaction tube, then treat it in a He inert atmosphere at 500°C for 2h, cool to 60°C and switch to 10% H 2 /Ar mixture, and heat up to 800°C (heating at 10°C ⁇ min -1 ), and finally detect its hydrogen consumption.
  • Catalyst performance evaluation The Fischer-Tropsch operation process is as follows: a certain amount of catalyst is placed in the middle of the stainless steel reaction tube, the reducing gas is turned on and a certain pressure is adjusted for reduction, and the temperature is adjusted to 450°C. After the reduction reaction was carried out for 16 hours, the reducing gas was turned off and the reaction furnace was quickly lowered to room temperature. Turn on the gas chromatography GC-9160 and GC-2060, and operate according to the operating procedures. Turn on the synthesis gas and adjust it to a constant flow rate, then heat the reaction furnace to a certain temperature, take samples every 5 hours, stop sampling for 60 hours after the reaction, and turn off the synthesis gas and gas chromatograph.
  • the reaction product can be analyzed and detected by gas chromatography: GC-9160 gas chromatograph detection: FID is used to detect C 1 -C 30 reaction products; unreacted synthesis gas and short-chain hydrocarbons can be detected by GC-2060 gas chromatograph : Use FID to detect CH 4 , C 2 H 6 , C 3 H 8 and C 4 H 10 ; Use TCD to detect H 2 , N 2 , CO, CH 4 and CO 2 .
  • Sinitial N2 , Sfinal N2 , Sinitial CO and Sfinal CO are respectively expressed as the peak areas of initial N 2 , final N 2 , initial CO and final CO in the TCD chromatogram.
  • S CH4 , S N2 , and f CH4 , f N2 are respectively expressed as the corresponding area peaks of CH 4 and N 2 in the TCD chromatogram and their internal standard factors.
  • the amount of various hydrocarbon product substances in the reaction product (expressed in terms of the amount of carbon atom-containing substances) in the reaction product is obtained by the proportional relationship of all products detected by gas chromatography. Then, with CH 4 as the second internal standard, the peak area of each hydrocarbon separated by FID is used to obtain the amount of each component in the product:
  • the hydrocarbon product selectivity is calculated by formula (5)
  • a method for preparing a cobalt-based catalyst supported by mesoporous carbon material GMC includes the following steps:
  • the mixture of SBA-15 and soybean oil was ball milled at 400 rpm ⁇ min -1 for 5 hours with a ball mill, then mixed uniformly, then the mixture was divided into three parts, and then transferred into In the quartz tube furnace, under the protection of N 2 , the temperature was raised to 700, 800 and 900 °C for carbonization for 5 hours at 4°C ⁇ min -1 to produce three kinds of materials calcined at different temperatures.
  • Comparative Example 1 The carbon material in Example 1 was replaced with mesoporous carbon CMK-3 and activated carbon AC
  • Example 1 The catalysts of Example 1 and Comparative Example 1 were tested for performance, and the specific test results are as follows:
  • FIG. 1 is the X-ray diffraction spectrum of the catalyst calcined with carbon support at different temperatures in Example 1.
  • FIG. 1 It can be seen from Figure 1 that the diffraction peak at 26.6° corresponds to the characteristic diffraction peak of graphitized carbon.
  • the mesopores with high calcining temperature Carbon materials have a high degree of graphitization.
  • the diffraction peaks at 36.4°, 42.3°, 61.6°, 73.9° and 77.8° belong to the characteristic diffraction peaks of different crystal planes of CoO (JCPDS 43-1004) on the catalyst surface.
  • Fig. 2 shows the Raman spectra of the catalysts calcined with carbon supports at different temperatures in Example 1. It can be seen from the figure that there are two scattering intensity peaks. The former is caused by single crystal graphite defects and is called D peak, and the latter is caused by the in-plane stretching vibration of carbon atom sp 2 hybridization, which is called G peak. . Under normal circumstances, the ratio of the area of the D peak to the G peak determines the degree of graphitization of the carbon material. The smaller the ratio of I D /I G (the area ratio of the two peaks), the degree of graphitization of the prepared carbon material. Higher.
  • the I D /I G ratios of Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 1.879, 1.744 and 1.550, respectively. Therefore, the graphite of Co/GMC-900 catalyst calcined at 900°C The degree of chemistry is higher. In addition, the increase in the calcination temperature of the carrier causes the peak to move in the direction of the short wave number, that is, a red shift occurs, which is caused by graphitization defects.
  • Fig. 3 is a transmission electron microscope photograph of the catalyst calcined on a carbon support at different temperatures in Example 1, (a) Co/GMC-700, (b) Co/GMC-800, and (c) Co/GMC-900. It can be seen from the figure that the cobalt metal particles are uniformly dispersed on the surface of the mesoporous carbon support and the inner surface of the pores. As the calcining temperature of the carbon material increases, the mesoporous structure of the carbon is destroyed.
  • 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 10.5 ⁇ 15.5nm, 9 ⁇ 12nm and 7 ⁇ 9nm, respectively. This is basically consistent with the particle size obtained by XRD.
  • FIG. 4 shows the nitrogen adsorption and desorption curves of the catalyst calcined with carbon support at different temperatures in Example 1.
  • capillary condensation begins to appear in the smallest hole.
  • the relative pressure P/P 0 gradually increased, capillary condensation gradually appeared in the mesopores until the pressure was saturated. The entire system was filled with condensation liquid, and a larger hysteresis loop appeared.
  • Fig. 5 is a pore size distribution curve of a catalyst calcined with a carbon support at different temperatures in Example 1. It can be seen from the figure that the pore diameters of the three catalysts Co/GMC-700, Co/GMC-800 and Co/GMC-900 are basically concentrated at 3.9nm.
  • Table 1 shows the specific surface area, pore diameter and average pore volume data of Co/GMC-700, Co/GMC-800 and Co/GMC-900 in Example 1. It can be seen from the table that the catalysts Co/GMC-700, Co The specific surface areas of /GMC-800 and Co/GMC-900 are 207m 2 .g -1 , 246m 2 .g -1 , and 306m 2 .g -1 respectively ; the catalysts Co/GMC, Co/GMC-800 and Co/GMC an average pore volume of -900 respectively 0.12cm 3 .g -1, 0.22cm 3 .g -1, 0.26cm 3 .g -1. It can be seen from the above that as the calcination temperature of the carbon support increases, the specific surface area and total volume of the catalyst continue to increase.
  • Table 1 The specific surface area, pore diameter and average pore volume data of Co/GMC-700, Co/GMC-800 and Co/GMC-900 in Example 1
  • Fig. 6 shows the H 2 -TPR patterns of the catalyst calcined with a carbon support at different temperatures in Example 1. It can be seen from the figure that all catalysts show three reduction peaks of hydrogen. The first reduction peak from left to right represents the hydrogen reduction peak of Co 3 O 4 ⁇ CoO, and the second represents the hydrogen reduction peak of CoO ⁇ Co. Reduction peak, the third represents the gasification peak of the carbon carrier. In addition, there is no reduction peak above 700°C, indicating that no hard-to-reducible compounds are formed on the surface of the catalyst.
  • the cobalt-based catalyst supported on a carbon support with a higher calcining temperature achieves a higher reduction temperature of the Co 3 O 4 ⁇ CoO ⁇ Co active phase, indicating that the carbon support calcined at a higher temperature is more conducive to increasing the mesoporous carbon
  • the interaction between the carrier and the cobalt is enhanced.
  • TEM combined with nitrogen physical adsorption and desorption BET analysis showed that the collapse of the mesoporous structure of the mesoporous carbon material introduced more physical defects, improved the dispersibility of cobalt on the mesoporous carbon support, and the reduction of the cobalt particle size increased
  • the interaction force with the carrier improves the stability of the catalyst.
  • Fig. 7 shows the change in CO conversion rate of the catalyst calcined with carbon support at different temperatures in Example 1 during the Fischer-Tropsch synthesis reaction. It can be seen from the figure that the carbon support calcined at a higher temperature has a higher CO conversion rate.
  • the specific surface area of Co/GMC-800 has a smaller growth relative to Co/GMC-700 and the particle size of Co/GMC-800 is larger.
  • the CO conversion rate of the Co/GMC-800 catalyst calcined at 800°C is relatively low. After 60 hours of catalyst performance evaluation of Co/GMC-700, Co/GMC-800 and Co/GMC-900, the CO conversion rate decreased from 45%, 37% and 55% to 35%, 26% and 42% respectively .
  • Table 2 shows the Fischer-Tropsch synthesis catalytic reaction performance of the Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts in Example 1. It can be seen from the table that the C 5+ of Co/GMC-900 has Higher selectivity, which may be due to its strong graphitization degree and graphite defects promote the electron transfer ability between the metal cobalt and CO, and then activate the CO molecules, so that the adsorbed CO molecules on the catalyst surface increase, which is beneficial to the formation of C 5 + A mixture of the above.
  • FIG. 8 shows the XRD after the Fischer-Tropsch synthesis reaction of the catalyst calcined with carbon support at different temperatures in Example 1.
  • FIG. 8 shows the 2 ⁇ values of the three obvious diffraction peaks of Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 42.5°, 45.7° and 68.3°, corresponding to Co 2 C(JCPDS 72-1369), while the other diffraction peaks of Co 3 C (JCPDS 89-2866) correspond to 60° of Co/GMC-700, 60° and 75° of Co/GMC-800, and Co/GMC-800. 60°, 75° and 83° of GMC-800.
  • Fig. 9 is a transmission electron microscope photograph of the catalyst Fischer-Tropsch synthesis reaction of the carbon support calcined at different temperatures in Example 1, (a) is Co/GMC-700, (b) is Co/GMC-800, (c) Co/ GMC-900. It can be seen from the figure that as the reaction time changes, the particle size of CoO particles continues to increase and agglomeration occurs; the particle sizes of CoO particles are 10.5-14nm, 12.5-17.5nm and 10-14nm, respectively.
  • FIG. 10 is a pore size distribution diagram of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1.
  • FIG. It can be seen from the figure that the pore size distributions of GMC-800, CMK-3 and AC are mainly concentrated in 3.6nm, 3.9nm and 3.9nm, which shows that the carbon materials prepared with SBA-15 as the hard template have orderly Mesoporous structure.
  • Fig. 11 is a TEM image of GMC-800 of Example 1 and CMK-3 of Comparative Example 1, (a) is GMC-800, and (b) is CMK-3. It can be seen from the figure that the prepared GMC-800 and CMK-3 have an ordered structure.
  • the absorption and desorption curve of AC is an I-type isotherm, which is a microporous structure.
  • the N 2 adsorption and desorption isotherm of the catalyst is similar to its corresponding support adsorption and desorption isotherm, which indicates that the structure and performance of the catalyst support change little during the preparation process.
  • Fig. 13 shows the nitrogen physical adsorption and desorption isotherms of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC carbon supports of Comparative Example 1 loaded with cobalt. It can be seen from the figure that the specific surface area, pore size and pore volume of CMK-3 are the largest among the three carbon support materials, which are respectively 939 m 2 .g -1 , 1.31 cm 3. G -1 and 5.57 nm. The specific surface area of AC and CMK-3 is higher than that of GMC-800.
  • the average pore diameter of CMK-3 is the largest (5.57nm), AC is the smallest (2.25nm), and GMC-800 is in the middle (5.57nm).
  • the specific surface area and pore volume of the support significantly decrease. It may be due to the cobalt oxide particles filling the pores on the surface of the carrier.
  • Table 3 shows the physical and chemical properties of the carbon material GMC-800 in Example 1 and the CMK-3 and AC in Comparative Example 1 before and after loading cobalt. It can be seen from the table that the specific surface area, pore size and pore volume of CMK-3 are the largest among the three carbon support materials, which are respectively 939m 2 .g -1 , 1.31cm 3 .g -1 and 5.57nm. The specific surface area of AC and CMK-3 is higher than that of GMC-800. Comparing the average pore diameter of the carrier, the average pore diameter of CMK-3 is the largest (5.57nm), AC is the smallest (2.25nm), and GMC-800 is in the middle (5.57nm). In addition, after 15wt.% cobalt is loaded on the corresponding carbon support, the specific surface area and pore volume of the support significantly decrease.
  • Table 3 shows the physical and chemical properties of carbon material GMC-800 in Example 1 and CMK-3 and AC in Comparative Example 1 before and after loading cobalt
  • FIG. 14 is an XRD pattern of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • FIG. It can be seen from the figure that the small-angle X-ray diffraction pattern of the mesoporous material mainly has diffraction peaks at 1 to 2, while the prepared catalysts Co/GMC-800 and Co/CMK-3 have diffraction peaks at 1.039. It shows that they have a mesoporous structure.
  • the average particle size of Co/GMC-800, Co/CMK-3 and Co/AC catalysts CoO calculated by Scherrer equation are 11.6nm, 6.9nm and 19.2nm, respectively.
  • Figure 15 shows the Raman spectra of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. It can be seen from the figure that there are two scattering intensity peaks on the Raman spectrum. The former is caused by single-crystal graphite defects, called D peaks, and the latter is caused by the in-plane stretching vibration of the sp 2 hybridization of carbon atoms. , Is called G peak. Under normal circumstances, the ratio of the area of the D peak to the G peak determines the degree of graphitization of the carbon material. The smaller the ratio of I D /I G (the area ratio of the two peaks), the degree of graphitization of the prepared carbon material. Higher.
  • Figure 16 is a transmission electron micrograph 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. (c) is Co/AC.
  • the catalysts Co/GMC-800 and Co/CMK-3 have a mesoporous structure. CoO particles are uniformly dispersed on the mesoporous carbon material GMC, and its structure is relatively regular; while the mesoporous carbon material CMK-3 is loaded with cobalt, its ordered mesoporous structure partially collapses, but the CoO nanoparticles can be uniformly dispersed in CMK-3 On the carrier.
  • CoO is relatively concentrated.
  • 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 9-12nm, 6.5-8nm and 12-17.5nm, respectively.
  • FIG. 17 shows the H 2 -TPR patterns of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • FIG. It can be seen from the figure that all catalysts show three reduction peaks of hydrogen.
  • the first reduction peak from left to right represents the hydrogen reduction peak of Co 3 O 4 ⁇ CoO
  • the second reduction peak represents the reduction peak of CoO ⁇ Co.
  • the hydrogen reduction peak, the third reduction peak represents the gasification peak of the carbon carrier.
  • There is no reduction peak above 700°C indicating that no hard-to-reducible compounds are formed on the surface of the catalyst.
  • This also shows that the interaction force between cobalt oxide and carbon support is better than that of oxide support (for example: SiO 2 and Al 2 O 3 The interaction force between) and the cobalt catalyst is much weaker.
  • Figure 18 shows the changes in the CO conversion rate of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 during the Fischer-Tropsch synthesis reaction. It can be seen from the figure that the stability of the three catalysts is different due to the influence of the structural properties of the support.
  • the catalytic activity of the catalyst Co/CMK-3 is relatively stable. After the catalytic reaction is carried out for 60 hours, the CO conversion rate has dropped from 21% by 15%, while the CO conversion rate of Co/GMC has dropped from 37% to 26%.
  • the CO conversion rate of Co/AC The conversion rate decreased by 9% from 19%.
  • Table 4 shows the Fischer-Tropsch synthesis catalytic reaction performance of the Co/GMC-800 of Example 1 and the Co/CMK-3 and Co/AC catalysts of Comparative Example 1. It can be seen from the table that Co/GMC-800 has a higher Conv. CO (29.4%), which may be due to the higher degree of graphitization of GMC-800, which facilitates the transfer of electrons between cobalt and CO and promotes CO activation. Although the Co/CMK-3 catalyst has a larger specific surface area and pore volume, the Conv. CO is only 18.05%, which may be due to the amorphous and poor graphitized structure of CMK-3 after cobalt loading. Caused by the destruction of part of the orderly structure.
  • the catalyst Co/GMC-800 is compared with the catalyst Co/CMK-3 and Co/ AC can obtain more C 5+ hydrocarbon products and lower methane and C 2 -C 4 . This may be due to the strong graphitization degree which promotes the electron transfer ability between the metal cobalt and CO, and then activates the CO molecules, which makes the CO molecules adsorbed on the catalyst surface increase, which is conducive to the formation of a mixture of C 5+ and above.
  • FIG. 19 shows the XRD after the Fischer-Tropsch synthesis reaction of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
  • FIG. It can be seen from the figure that the 2 ⁇ values of the three obvious diffraction peaks of Co/GMC and Co/CMK-3 are 42.5°, 45.7° and 68.3°, which correspond to the characteristic diffraction peaks of Co 2 C (JCPDS 72-1369). The other two diffraction peaks correspond to Co 3 C (JCPDS89-2866), and their 2 ⁇ values are 60° and 75°.
  • Example 20 is a transmission electron microscope photograph of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 after the Fischer-Tropsch synthesis reaction. It can be seen from the figure that as the reaction time changes, the particle size of CoO particles increases continuously and agglomerates.
  • 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 12.5 to 17.5 nm, 12 to 17 nm and 15 to 25 nm, respectively. This also confirmed the reason why the CO conversion rate of the catalyst decreased rapidly after doping with nitrogen.

Abstract

The present invention relates to the technical field of metal catalysts, and provides a mesoporous carbon material loaded cobalt-based catalyst and a preparation method therefor. The preparation method for the cobalt-based catalyst comprises: (1) dissolving Co(NO 3) 2•6H 2O into an absolute ethanol solution; (2) soaking a mesoporous carbon material GMC into the solution in step (1), and then evaporating same in a rotary evaporator to obtain a mixture; and (3) placing the mixture in step (2) into an oven for drying, and then calcining same to obtain the catalyst. The catalyst is higher in graphitization degree, more uniform in CoO particle dispersion, higher in CO conversion rate, lower in CO 2 generation rate, and better in C 5+ selectivity.

Description

一种介孔碳材料负载的钴基催化剂及其制备方法Cobalt-based catalyst supported by mesoporous carbon material and preparation method thereof 技术领域Technical field
本发明涉及一种介孔碳材料负载的钴基催化剂及其制备方法，属于金属催化剂技术领域。The invention relates to a cobalt-based catalyst supported by a mesoporous carbon material and a preparation method thereof, and belongs to the technical field of metal catalysts.
背景技术Background technique
工业革命以来，人类对能源的需求不断增加，而石油、煤等非再生资源的有限性迫使人们寻求新的能源，例如核能、风能、太阳能等都是研究讨论的热门话题。其中，生物质便是核心话题之一，它具有来源广泛、种类繁多、发展潜力大等优势。人们利用生物质将其转化为燃料、电能等不仅解决了能源问题，还能将一些废弃生物质资源化再利用。Since the industrial revolution, human demand for energy has continued to increase, and the limitation of non-renewable resources such as oil and coal has forced people to seek new energy sources, such as nuclear energy, wind energy, and solar energy, which are hot topics of research and discussion. Among them, biomass is one of the core topics. It has the advantages of wide sources, wide variety, and great development potential. People use biomass to convert it into fuel, electricity, etc., not only to solve the energy problem, but also to reuse some waste biomass.
多孔碳材料不仅具有碳材料的耐酸碱高温、化学性质稳定和廉价等优势，还具有孔道结构规则、比表面积大、孔径可调等的优良性质。Porous carbon materials not only have the advantages of carbon materials such as acid and alkali resistance, high temperature resistance, stable chemical properties, and low cost, but also have excellent properties such as regular pore structure, large specific surface area, and adjustable pore size.
目前利用硬模板法制备多孔碳材料具有较高的比表面积和孔容、大的孔径，但是这种多孔碳材料在实际应用中也存在一定的局限性，比如：制备的材料复制了模板剂的结构但不能任意改变。At present, the use of hard template method to prepare porous carbon materials has a higher specific surface area, pore volume, and large pore diameter. However, this porous carbon material also has certain limitations in practical applications, such as: the prepared material replicates the template The structure cannot be changed arbitrarily.
在费托催化反应中，载体的选用与催化剂的催化性能密切相关。载体与金属之间相互作用过强，则会影响金属的分散性能，且不利于金属的还原；反之，则降低了金属的稳定性。In the Fischer-Tropsch catalytic reaction, the choice of carrier is closely related to the catalytic performance of the catalyst. If the interaction between the support and the metal is too strong, it will affect the dispersibility of the metal and is not conducive to the reduction of the metal; on the contrary, it will reduce the stability of the metal.
目前，对于费-托反应钴基催化剂的活性相为单质钴。在催化剂表面获得高分散和高还原的单质钴颗粒是提高钴基催化剂反应效率的关键。为了提高钴物种的分散度，很多研究工作采用高比表面、孔道发达的载体如TiO 2、Al 2O 3、SiO 2等来负载活性组分。但是该类载体与活性组分易形成难还原物种，导致在催化剂表面难以获得高分散度和高还原度相统一的活性相。 At present, the active phase of the cobalt-based catalyst 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. In order to improve the dispersion of cobalt species, many research works have used carriers with high specific surface and well-developed pores, such as TiO 2 , Al 2 O 3 , and SiO 2 to support active components. However, this type of carrier and active components are prone to form difficult-to-reducible species, which makes it difficult to obtain a unified active phase with high dispersion and high reduction on the surface of the catalyst.
发明内容Summary of the invention
为了解决上述至少一个问题，本发明提供了一种介孔碳材料负载的钴基催化剂及其制备方法。本发明的催化剂具有更高的CO转化率和更好的催化反应性能；在C 5+的选择性方面有显著提高。 In order to solve at least one of the above-mentioned problems, the present invention provides a cobalt-based catalyst supported by mesoporous carbon materials and a preparation method thereof. The catalyst of the present invention has a higher CO conversion rate and better catalytic reaction performance; the C 5+ selectivity is significantly improved.
本发明的第一个目的是提供一种介孔碳材料的制备方法，具体步骤为：The first object of the present invention is to provide a method for preparing mesoporous carbon material, the specific steps are:
S1：采用固-液球磨模板法将SBA-15与大豆油混合均匀；S1: Use solid-liquid ball mill template method to mix SBA-15 and soybean oil evenly;
S2：将S1的混合物转入石英管式炉中，升温至700-900℃碳化；S2: Transfer the mixture of S1 into a quartz tube furnace and heat up to 700-900°C for carbonization;
S3：将S2的混合物用NaOH溶液刻蚀，即可得到所述的介孔碳材料，标记为介孔碳材料GMC。S3: The mixture of S2 is etched with NaOH solution to obtain the mesoporous carbon material, which is marked as mesoporous carbon material GMC.
在一种实施方式中，S1所述的SBA-15与大豆油混合物的质量比为1:2。In one embodiment, the mass ratio of SBA-15 and soybean oil mixture described in S1 is 1:2.
在一种实施方式中，S1所述的混合方式为：用球磨机在400rpm·min -1转速下球磨5h。 In one embodiment, the mixing method described in S1 is: ball milling with a ball mill at a speed of 400 rpm·min -1 for 5 hours.
在一种实施方式中，S2所述的碳化过程具体为：在N 2保护下，升温速率为：4℃·min -1，碳化时间为5h。 In one embodiment, the carbonization process described in S2 is specifically: under the protection of N 2 , the heating rate is 4° C.·min -1 , and the carbonization time is 5 h.
在一种实施方式中，S3所述的NaOH溶液的浓度为2mol/L。In one embodiment, the concentration of the NaOH solution described in S3 is 2 mol/L.
在一种实施方式中，S3所述的刻蚀次数为3次，每次刻蚀时间为24h。In one embodiment, the number of etchings described in S3 is 3 times, and each etching time is 24 hours.
在一种实施方式中，所述的SBA-15的制备方法为：首先将3.0g表面活性剂P123和3.0g的丙三醇混匀后，加入到115.0mL稀盐酸溶液(1.5mol.L -1)后在37℃水浴锅中搅拌透明，3h后剧烈搅拌并逐滴滴加6.45g正硅酸二乙酯(TEOS)，加完后剧烈搅拌5min；然后将混合液在37℃的水浴中静置24h，取出混合物放入110℃的烘箱中12h；待冷却至室温，将得到的白色固体反复抽滤、洗涤到pH＝7，再用无水乙醇洗涤2～3次，然后将产品放入80℃的烘箱中烘干后，放入马弗炉中在550℃焙烧5h(升温速率3℃·min -1)，最终制备出了有序介孔材料SBA-15。 In one embodiment, the preparation method of SBA-15 are as follows: First, 3.0g of surfactant P123 3.0g of glycerin and after mixing, was added to a dilute hydrochloric acid solution 115.0mL (1.5mol.L - 1 ) Then stir in a 37°C water bath for transparency. After 3 hours, stir vigorously and add 6.45g diethyl orthosilicate (TEOS) dropwise. After the addition, stir vigorously for 5 minutes; then put the mixture in a 37°C water bath Let stand for 24 hours, take out the mixture and put it in an oven at 110°C for 12 hours; after cooling to room temperature, the white solid obtained is repeatedly suction filtered and washed to pH=7, and then washed with absolute ethanol for 2 to 3 times, and then the product is placed After being dried in an oven at 80°C, it was put into a muffle furnace and fired at 550°C for 5 hours (heating rate 3°C·min -1 ), and finally an ordered mesoporous material SBA-15 was prepared.
本发明的第二个目的是提供一种本发明的制备方法得到的介孔碳材料GMC。The second object of the present invention is to provide a mesoporous carbon material GMC obtained by the preparation method of the present invention.
本发明的第三个目的是提供一种包含本发明所述的介孔碳材料GMC负载的钴基催化剂。The third object of the present invention is to provide a cobalt-based catalyst containing the mesoporous carbon material GMC supported by the present invention.
本发明的第四个目的是提供一种本发明所述的介孔碳材料GMC负载的钴基催化剂的制备方法，包括以下步骤：The fourth object of the present invention is to provide a method for preparing the mesoporous carbon material GMC-supported cobalt-based catalyst of the present invention, which includes the following steps:
(1)将Co(NO 3) 2·6H 2O溶于无水乙醇溶液中； (1) Dissolve Co(NO 3 ) 2 ·6H 2 O in anhydrous ethanol solution;
(2)将介孔碳材料GMC浸入步骤(1)的溶液中，然后在旋转蒸发仪中蒸发，得到混合物；(2) Immerse the mesoporous carbon material GMC in the solution of step (1), and then evaporate in a rotary evaporator to obtain a mixture;
(3)将步骤(2)的混合物放入烘箱中干燥；然后煅烧，即可以得到所述的催化剂。(3) Put the mixture of step (2) into an oven to dry; then calcinate, and then the catalyst can be obtained.
在一种实施方式中，步骤(1)所述的Co(NO 3) 2·6H 2O和步骤(2)所述的介孔碳材料质量比为1.08：1。 In one embodiment, the mass ratio of the Co(NO 3 ) 2 ·6H 2 O described in step (1) and the mesoporous carbon material described in step (2) is 1.08:1.
在一种实施方式中，步骤(1)所述的Co(NO 3) 2·6H 2O和无水乙醇的质量比为1：5-50。 In one embodiment, the mass ratio of Co(NO 3 ) 2 ·6H 2 O and absolute ethanol mentioned in step (1) is 1:5-50.
在一种实施方式中，步骤(2)所述的浸入时间为1-2min。In one embodiment, the immersion time in step (2) is 1-2 min.
在一种实施方式中，步骤(2)所述的旋转蒸发仪的温度为35℃，蒸发时间为5-40min。In one embodiment, the temperature of the rotary evaporator described in step (2) is 35° C., and the evaporation time is 5-40 min.
在一种实施方式中，步骤(3)所述的干燥温度为50℃干燥2-7h。In one embodiment, the drying temperature in step (3) is 50°C for 2-7 hours.
在一种实施方式中，步骤(3)所述的煅烧具体为：在N 2氛围下煅烧350℃，升温速率为3℃·min -1，煅烧时间为2-10h。 In one embodiment, the calcination described in step (3) is specifically: calcination at 350° C. in an N 2 atmosphere, a heating rate of 3° C.·min -1 , and a calcination time of 2-10 h.
本发明的第五个目的是本发明所述的介孔碳材料GMC在催化、电化学、环境或磁催化领域中的应用。The fifth objective of the present invention is the application of the mesoporous carbon material GMC of the present invention in the fields of catalysis, electrochemistry, environment or magnetocatalysis.
本发明的第六个目的是本发明所述的催化剂在工业制氢中的应用。The sixth object of the present invention is the application of the catalyst of the present invention in industrial hydrogen production.
本发明的有益效果：The beneficial effects of the present invention:
(1)本发明以生物质(大豆油)为碳源，通过简单的一步固-液球磨法制备出了介孔碳材料GMC负载的钴基催化剂，制备方法简单，环保。(1) In the present invention, biomass (soybean oil) is used as a carbon source to prepare a mesoporous carbon material GMC-supported cobalt-based catalyst through a simple one-step solid-liquid ball milling method, and the preparation method is simple and environmentally friendly.
(2)本发明制备出的石墨化介孔碳材料GMC介孔结构规整有序，孔容和比表面积相对较大，孔径分布相对集中。(2) The graphitized mesoporous carbon material GMC prepared by the present invention has a regular and orderly mesoporous structure, relatively large pore volume and specific surface area, and relatively concentrated pore size distribution.
(3)本发明的Co/GMC催化剂中石墨化程度更高、CoO颗粒分散更均匀，有更高的CO转化率和更低的CO 2生成率，且C 5+的选择性更好，显示Co/GMC用于费托合成催化剂良好性能。 (3) The Co/GMC catalyst of the present invention has a higher degree of graphitization, a more uniform dispersion of CoO particles, a higher CO conversion rate and a lower CO 2 generation rate, and the C 5+ selectivity is better, showing Co/GMC is used for Fischer-Tropsch synthesis catalyst with good performance.
附图说明Description of the drawings
图1为实施例1中不同温度锻烧碳载体的催化剂的X射线衍射谱图。FIG. 1 is the X-ray diffraction spectrum of the catalyst calcined with carbon support at different temperatures in Example 1. FIG.
图2为实施例1的不同温度锻烧碳载体的催化剂的拉曼光谱。Fig. 2 shows the Raman spectra of the catalysts calcined with carbon supports at different temperatures in Example 1.
图3为实施例1的不同温度锻烧碳载体的催化剂的透射电子显微镜照片，(a)为Co/GMC-700，(b)为Co/GMC-800，(c)Co/GMC-900。Fig. 3 is a transmission electron microscope photograph of the catalyst calcined on a carbon support at different temperatures in Example 1, (a) Co/GMC-700, (b) Co/GMC-800, and (c) Co/GMC-900.
图4为实施例1的不同温度锻烧碳载体的催化剂的氮气吸脱附曲线。4 shows the nitrogen adsorption and desorption curves of the catalyst calcined with carbon support at different temperatures in Example 1. FIG.
图5为实施例1的不同温度锻烧碳载体的催化剂的孔径分布曲线Figure 5 is the pore size distribution curve of the catalyst calcined with carbon support at different temperatures in Example 1
图6为实施例1的不同温度锻烧碳载体的催化剂的H 2-TPR图谱。 Fig. 6 shows the H 2 -TPR patterns of the catalyst calcined with a carbon support at different temperatures in Example 1.
图7为实施例1的不同温度锻烧碳载体的催化剂在费托合成反应过程中CO转化率的变化。Fig. 7 shows the change in CO conversion rate of the catalyst calcined with carbon support at different temperatures in Example 1 during the Fischer-Tropsch synthesis reaction.
图8为实施例1的不同温度锻烧碳载体的催化剂费托合成反应后的XRD。FIG. 8 shows the XRD after the Fischer-Tropsch synthesis reaction of the catalyst calcined with carbon support at different temperatures in Example 1. FIG.
图9为实施例1的不同温度锻烧碳载体的催化剂费托合成反应后透射电子显微镜照片，(a)为Co/GMC-700，(b)为Co/GMC-800，(c)Co/GMC-900。Fig. 9 is a transmission electron microscope photograph of the catalyst Fischer-Tropsch synthesis reaction of the carbon support calcined at different temperatures in Example 1, (a) is Co/GMC-700, (b) is Co/GMC-800, (c) Co/ GMC-900.
图10为实施例1的GMC-800和对照例1的CMK-3、AC的孔径分布图。FIG. 10 is a pore size distribution diagram of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1. FIG.
图11为实施例1的GMC-800和对照例1的CMK-3的TEM图，(a)为GMC-800，(b)为CMK-3。Fig. 11 is a TEM image of GMC-800 of Example 1 and CMK-3 of Comparative Example 1, (a) is GMC-800, and (b) is CMK-3.
图12为实施例1的GMC-800和对照例1的CMK-3、AC的氮气物理吸脱附曲线。Figure 12 shows the nitrogen physical adsorption and desorption curves of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1.
图13为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC碳载体负载钴后的氮气物理吸附脱附等温曲线。Fig. 13 shows the physical adsorption and desorption isotherms of nitrogen after Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC carbon supports of Comparative Example 1 loaded with cobalt.
图14为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的XRD图。FIG. 14 is an XRD pattern of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG.
图15为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的拉曼光谱。Figure 15 shows the Raman spectra of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1.
图16为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的透射电子显微镜照片；(a)为Co/GMC-800，(b)为Co/CMK-3，(c)为Co/AC。Figure 16 is a transmission electron micrograph 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. (c) is Co/AC.
图17为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的H 2-TPR图谱。 FIG. 17 shows the H 2 -TPR patterns of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG.
图18为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC在费托合成反应过程中CO转化率的变化。Figure 18 shows the changes in the CO conversion rate of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 during the Fischer-Tropsch synthesis reaction.
图19为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的费托合成反应后的XRD。FIG. 19 shows the XRD after the Fischer-Tropsch synthesis reaction of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG.
图20为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的费托合成反应后的透射电子显微镜照片。20 is a transmission electron microscope photograph of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 after the Fischer-Tropsch synthesis reaction.
具体实施方式Detailed ways
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。The preferred embodiments of the present invention are described below, and it should be understood that the embodiments are for better explaining the present invention and are not used to limit the present invention.
X-射线粉末衍射：利用XRD可有效的确定实测物质结构。由于不同的物质其结构性能不同，因此，可以结合实测物质的点阵晶面间距、衍射特征峰强度与标准PDF卡进行对比，进而确定出实测物质的物相组成。另外，由于不同的物质其衍射峰强度、衍射峰所处的位置不同，可以以此结合XRD图谱分析确定其结构参数信息。采用CuKα为辐射源，管压为40KV，管电流为200mA，扫描范围(2θ)为10°～80°，扫描步长为0.02°。通过谢乐公式计算得到：X-ray powder diffraction: XRD can effectively determine the structure of the measured substance. Because different materials have different structural properties, the lattice spacing and diffraction characteristic peak intensity of the measured material can be compared with the standard PDF card to determine the phase composition of the measured material. In addition, because different substances have different diffraction peak intensities and different positions of diffraction peaks, it can be combined with XRD pattern analysis to determine their structural parameter information. Using CuKα as the radiation source, the tube pressure is 40KV, the tube current is 200mA, the scanning range (2θ) is 10°～80°, and the scanning step length is 0.02°. Calculated by the Xie Le formula:
Figure PCTCN2020134712-appb-000001
Figure PCTCN2020134712-appb-000001
其中D表示为晶粒粒径；K表示为谢乐常数，β表示为衍射峰半峰宽；λ表示为入射X射线波长，θ表示为衍射角。Where D is the grain size; K is the Scherrer constant, β is the half-width of the diffraction peak; λ is the incident X-ray wavelength, and θ is the diffraction angle.
透射电子显微镜：以波长很短的电子束为光源，然后将其加速聚集投射于实测样品上，电子与样品中的原子发生碰撞而改变方向，从而产生立体散射，最终将所产生的影响放大展现在成像器件上。制样：超声样品+无水乙醇混合液，然后滴加到碳膜铜网上，干燥后测试。Transmission electron microscope: Use electron beam with a short wavelength as the light source, and then accelerate it to gather and project it on the measured sample. The electrons collide with the atoms in the sample to change the direction, thereby generating three-dimensional scattering, and finally magnifying the impact. On the imaging device. Sample preparation: ultrasonic sample + absolute ethanol mixture, then drip it on the carbon film copper net, and test after drying.
氮气物理吸附脱附：氮气的吸脱附测定孔径分布是一种比较成熟且常见的方法。它可以有效测出催化剂的比表面积、孔径和孔容等物理结构特性。Nitrogen physical adsorption and desorption: Nitrogen adsorption and desorption is a relatively mature and common method to determine the pore size distribution. It can effectively measure the physical structure characteristics of the catalyst such as specific surface area, pore size and pore volume.
拉曼光谱：测试仪器：Dilor Labram-1B光谱仪，以He-Ne为激发光源，其波长632.8nm，测试范围为1mm。Raman spectroscopy: Test instrument: Dilor Labram-1B spectrometer, with He-Ne as the excitation light source, its wavelength is 632.8nm, and the test range is 1mm.
H 2程序升温还原(H 2-TPR)：在U型石英反应管放置0.05g样品，然后在He惰性气氛500度处理2h，冷却至60℃切换为10％H 2/Ar混合气，升温至800℃(以10℃·min -1升温)， 最后检测其耗氢量。 H 2 temperature-programmed reduction (H 2 -TPR): Place 0.05g sample in a U-shaped quartz reaction tube, then treat it in a He inert atmosphere at 500°C for 2h, cool to 60°C and switch to 10% H 2 /Ar mixture, and heat up to 800°C (heating at 10°C·min -1 ), and finally detect its hydrogen consumption.
催化剂的性能评价：费托操作流程如下：将一定量的催化剂置于不锈钢反应管中部，打开还原气并调节一定压力进行还原，调温度升到450℃升。还原反应进行16h后，关闭还原气并将反应炉快速降至室温。打开气相色谱GC-9160和GC-2060，并按操作规程操作。打开合成气并调控至恒定流速，然后加热反应炉至一定温度，每隔5h采一次样，反应60h停止采样并关闭合成气和气相色谱。反应产物可通过气相色谱进行分析检测：GC-9160型气相色谱仪检测：采用FID检测C 1-C 30反应产物；未反应的合成气以及短链烃可通过GC-2060型气相色谱仪进行检测：采用FID检测CH 4、C 2H 6、C 3H 8和C 4H 10；采用TCD检测H 2、N 2、CO、CH 4和CO 2。 Catalyst performance evaluation: The Fischer-Tropsch operation process is as follows: a certain amount of catalyst is placed in the middle of the stainless steel reaction tube, the reducing gas is turned on and a certain pressure is adjusted for reduction, and the temperature is adjusted to 450°C. After the reduction reaction was carried out for 16 hours, the reducing gas was turned off and the reaction furnace was quickly lowered to room temperature. Turn on the gas chromatography GC-9160 and GC-2060, and operate according to the operating procedures. Turn on the synthesis gas and adjust it to a constant flow rate, then heat the reaction furnace to a certain temperature, take samples every 5 hours, stop sampling for 60 hours after the reaction, and turn off the synthesis gas and gas chromatograph. The reaction product can be analyzed and detected by gas chromatography: GC-9160 gas chromatograph detection: FID is used to detect C 1 -C 30 reaction products; unreacted synthesis gas and short-chain hydrocarbons can be detected by GC-2060 gas chromatograph : Use FID to detect CH 4 , C 2 H 6 , C 3 H 8 and C 4 H 10 ; Use TCD to detect H 2 , N 2 , CO, CH 4 and CO 2 .
具体性能评价如下：The specific performance evaluation is as follows:
1)根据碳平衡来计算CO的转化率(以N 2为内标)： 1) Calculate the conversion rate of CO based on the carbon balance (using N 2 as the internal standard):
Figure PCTCN2020134712-appb-000002
Figure PCTCN2020134712-appb-000002
(2)式中，S 初N2、S 终N2、和S 初CO、S 终CO分别表示为TCD色谱中所对应的初始N 2、最终N 2和初始CO、最终CO的峰面积。 (2) In the formula, Sinitial N2 , Sfinal N2 , Sinitial CO and Sfinal CO are respectively expressed as the peak areas of initial N 2 , final N 2 , initial CO and final CO in the TCD chromatogram.
2)CH 4产物的量： 2) The amount of CH 4 product:
根据TDX-01柱分离后的N 2和CH 4的峰面积，可以求出反应中生成的CH 4的物质的量。 Based on the peak areas of N 2 and CH 4 after separation on the TDX-01 column, the amount of CH 4 produced in the reaction can be calculated.
Figure PCTCN2020134712-appb-000003
Figure PCTCN2020134712-appb-000003
式中(3)，S CH4、S N2、和f CH4、f N2分别表示为TCD色谱中所对应的CH 4和N 2的面积峰及它们的内标因子。 In the formula (3), S CH4 , S N2 , and f CH4 , f N2 are respectively expressed as the corresponding area peaks of CH 4 and N 2 in the TCD chromatogram and their internal standard factors.
3)C n产物的选择性： 3) The selectivity of C n products:
通过气相色谱检测到的所有产物的比例关系求出反应产物中各种烃类产物物质的量(以含碳原子物质的量来表示)。然后以CH 4为第二内标，由FID分离后的各个烃的峰面积，分别得到产物中各组分物质的量： The amount of various hydrocarbon product substances in the reaction product (expressed in terms of the amount of carbon atom-containing substances) in the reaction product is obtained by the proportional relationship of all products detected by gas chromatography. Then, with CH 4 as the second internal standard, the peak area of each hydrocarbon separated by FID is used to obtain the amount of each component in the product:
Figure PCTCN2020134712-appb-000004
Figure PCTCN2020134712-appb-000004
烃产生物选择性由公式(5)计算得出The hydrocarbon product selectivity is calculated by formula (5)
Figure PCTCN2020134712-appb-000005
Figure PCTCN2020134712-appb-000005
实施例1Example 1
一种介孔碳材料GMC负载的钴基催化剂的制备方法，包括以下步骤：A method for preparing a cobalt-based catalyst supported by mesoporous carbon material GMC includes the following steps:
(1)有序介孔碳材料(GMC)的制备：(1) Preparation of ordered mesoporous carbon material (GMC):
采用固-液球磨模板法将SBA-15与大豆油混合物(质量比为1:2)用球磨机在400rpm·min -1转速下球磨5h后混合均匀，然后将混合物分为三份，先后转入石英管式炉中，在N 2保护下以4℃·min -1分别升温至700、800和900℃碳化5h，制成三种不同温度煅烧的材料。用NaOH溶液(浓度2mol/L)刻蚀3次，每次刻蚀时间为24h，以此除去硬模板剂SBA-15，最终得到不同温度下煅烧的多孔材料，分别标记为GMC-700、GMC-800、GMC-900。 Using the solid-liquid ball mill template method, the mixture of SBA-15 and soybean oil (mass ratio 1:2) was ball milled at 400 rpm·min -1 for 5 hours with a ball mill, then mixed uniformly, then the mixture was divided into three parts, and then transferred into In the quartz tube furnace, under the protection of N 2 , the temperature was raised to 700, 800 and 900 ℃ for carbonization for 5 hours at 4℃·min -1 to produce three kinds of materials calcined at different temperatures. Use NaOH solution (concentration 2mol/L) to etch 3 times, each etching time is 24h, in order to remove the hard template SBA-15, and finally obtain porous materials calcined at different temperatures, marked as GMC-700, GMC -800, GMC-900.
(2)浸渍法制备GMC-700、GMC-800、GMC-900催化剂：(2) Preparation of GMC-700, GMC-800, GMC-900 catalysts by impregnation method:
取0.8719g Co(NO 3) 2·6H 2O溶于过量的无水乙醇溶液，然后将0.8g多孔碳材料(GMC-700、GMC-800、GMC-900)浸入过量的硝酸钴乙醇溶液中，随后在旋转蒸发仪品中35℃下缓慢蒸发，然后将样品放入烘箱中50℃干燥。最后，将催化剂在N 2氛下煅烧350℃(以3℃·min -1升温)，最终分别得到三种催化剂Co/GMC-700、Co/GMC-800、Co/GMC-900。 Take 0.8719g Co(NO 3 ) 2 ·6H 2 O and dissolve it in excess absolute ethanol solution, and then immerse 0.8g porous carbon materials (GMC-700, GMC-800, GMC-900) into excess cobalt nitrate ethanol solution , And then slowly evaporate in a rotary evaporator at 35°C, and then put the sample in an oven at 50°C to dry. Finally, the catalyst was calcined at 350°C under N 2 atmosphere (heating at 3°C·min -1 ), and finally three catalysts Co/GMC-700, Co/GMC-800, and Co/GMC-900 were obtained.
对照例1：实施例1中的碳材料替换为介孔碳CMK-3、活性碳ACComparative Example 1: The carbon material in Example 1 was replaced with mesoporous carbon CMK-3 and activated carbon AC
(1)有序介孔碳CMK-3合成制备：(1) Synthesis and preparation of ordered mesoporous carbon CMK-3:
取9g SBA-15与45mL蔗糖浓硫酸混合液(质量比为9:1)充分混合均匀后，分别在110℃和160℃下各烘6h。烘干后将所得固体再次与45mL蔗糖浓硫酸混合液(质量比为9:1)混合，再在110℃和160℃下各烘6h。然后N 2保护下以4℃·min -1升温至900℃碳化5h，之后将碳化后样品用2mol/L NaOH溶液充分处理，抽滤后用去离子水洗涤2～3遍，最后100℃下烘干。 Take 9g of SBA-15 and 45mL of sucrose concentrated sulfuric acid mixture (mass ratio of 9:1) and mix them thoroughly, and then bake them at 110°C and 160°C for 6 hours. After drying, the obtained solid was mixed with 45 mL of sucrose concentrated sulfuric acid mixture (mass ratio of 9:1), and then baked at 110°C and 160°C for 6 hours. Then, under the protection of N 2 , the temperature is raised to 900 ℃ for carbonization for 5 hours at 4 ℃·min -1 , then the carbonized sample is fully treated with 2mol/L NaOH solution, filtered and washed with deionized water for 2 to 3 times, and finally at 100 ℃ drying.
(2)催化剂的制备：(2) Preparation of catalyst:
取0.8719g Co(NO 3) 2·6H 2O溶于过量的无水乙醇溶液，然后将0.8g碳材料(介孔碳CMK-3、活性碳AC)浸入过量的硝酸钴乙醇溶液中，随后在旋转蒸发仪中35℃下缓慢蒸发，然后将样品放入烘箱中50℃干燥。最后，将催化剂在N 2氛下煅烧350℃(以3℃·min -1升温)，最终分别得到两种催化剂Co/CMK-3、Co/AC。 Take 0.8719g of Co(NO 3 ) 2 ·6H 2 O and dissolve it in an excess of absolute ethanol solution, then immerse 0.8g of carbon materials (mesoporous carbon CMK-3, activated carbon AC) into the excess ethanol solution of cobalt nitrate, and then Slowly evaporate in a rotary evaporator at 35°C, and then put the sample in an oven at 50°C to dry. Finally, the catalyst was calcined at 350°C under N 2 atmosphere (increased at 3°C·min -1 ), and finally two catalysts, Co/CMK-3 and Co/AC, were obtained respectively.
将实施例1和对照例1的催化剂进行性能测试，具体测试结果如下：The catalysts of Example 1 and Comparative Example 1 were tested for performance, and the specific test results are as follows:
图1为实施例1中不同温度锻烧碳载体的催化剂的X射线衍射谱图。从图1可以看出：在26.6°处的衍射峰对应于石墨化碳的特征衍射峰，对比不同温度锻烧碳载体后负载的钴基催化剂XRD衍射峰的可见，锻烧温度高的介孔碳材料其石墨化程度高。而在36.4°、42.3°、61.6°、73.9°和77.8°衍射峰属于催化剂表面CoO(JCPDS 43-1004)不同晶面的特征衍射峰。载体表面 上只有CoO存在，不存在其他钴的氧化物。此外，不同温度锻烧下介孔碳的钴基催化剂上所形成的CoO峰的强度不同，说明CoO颗粒的大小也不同，显示了碳载体本身结构如石墨化程度、孔隙度大小等对颗粒大小造成的影响。通过谢乐公式计算出在700、800、900℃温度锻烧后的碳载体负载的钴基催化剂中CoO的平均颗粒大小分别为10.1、11.6、8.1nm。FIG. 1 is the X-ray diffraction spectrum of the catalyst calcined with carbon support at different temperatures in Example 1. FIG. It can be seen from Figure 1 that the diffraction peak at 26.6° corresponds to the characteristic diffraction peak of graphitized carbon. Compared with the XRD diffraction peaks of the cobalt-based catalyst supported after the carbon support is calcined at different temperatures, it can be seen that the mesopores with high calcining temperature Carbon materials have a high degree of graphitization. The diffraction peaks at 36.4°, 42.3°, 61.6°, 73.9° and 77.8° belong to the characteristic diffraction peaks of different crystal planes of CoO (JCPDS 43-1004) on the catalyst surface. Only CoO is present on the surface of the support, and no other cobalt oxides are present. In addition, the intensities of the CoO peaks formed on the mesoporous carbon cobalt-based catalysts calcined at different temperatures are different, indicating that the size of the CoO particles is also different, indicating that the structure of the carbon support itself, such as the degree of graphitization, porosity, etc. The impact. The average particle size of CoO in the carbon-supported cobalt-based catalysts calcined at 700, 800, and 900°C was calculated by the Scherer formula to be 10.1, 11.6, and 8.1 nm, respectively.
图2为实施例1的不同温度锻烧碳载体的催化剂的拉曼光谱。从图中看出：2个散射强度峰，前者是由单晶石墨缺陷引起的，被称为D峰，后者是由碳原子sp 2杂化的面内伸缩振动引起，被称为G峰。通常情况下，D峰与G峰的面积之比决定了碳材料的石墨化程度，I D/I G(两个峰的面积比)比值越小，则说明所制备出的碳材料石墨化程度越高。Co/GMC-700、Co/GMC-800、Co/GMC-900的I D/I G的比值分别为1.879、1.744和1.550，因此，在900℃锻烧下的Co/GMC-900催化剂的石墨化程度更高。另外，载体锻烧温度的增高，使得峰向短波数方向移动，即发生了红移，这是由于石墨化缺陷引起。 Fig. 2 shows the Raman spectra of the catalysts calcined with carbon supports at different temperatures in Example 1. It can be seen from the figure that there are two scattering intensity peaks. The former is caused by single crystal graphite defects and is called D peak, and the latter is caused by the in-plane stretching vibration of carbon atom sp 2 hybridization, which is called G peak. . Under normal circumstances, the ratio of the area of the D peak to the G peak determines the degree of graphitization of the carbon material. The smaller the ratio of I D /I G (the area ratio of the two peaks), the degree of graphitization of the prepared carbon material. Higher. The I D /I G ratios of Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 1.879, 1.744 and 1.550, respectively. Therefore, the graphite of Co/GMC-900 catalyst calcined at 900℃ The degree of chemistry is higher. In addition, the increase in the calcination temperature of the carrier causes the peak to move in the direction of the short wave number, that is, a red shift occurs, which is caused by graphitization defects.
图3为实施例1的不同温度锻烧碳载体的催化剂的透射电子显微镜照片，(a)为Co/GMC-700，(b)为Co/GMC-800，(c)Co/GMC-900。从图中可以看出：钴金属颗粒均匀地分散在介孔碳载体表面及孔道内表面上，随着碳材料锻烧温度的升高，碳的介孔结构被破坏。另外，通过TEM得出的粒径分布图，Co/GMC-700、Co/GMC-800、Co/GMC-900中CoO的颗粒粒径分别为10.5～15.5nm，9～12nm和7～9nm，这与XRD所得到的粒径大小也基本一致。Fig. 3 is a transmission electron microscope photograph of the catalyst calcined on a carbon support at different temperatures in Example 1, (a) Co/GMC-700, (b) Co/GMC-800, and (c) Co/GMC-900. It can be seen from the figure that the cobalt metal particles are uniformly dispersed on the surface of the mesoporous carbon support and the inner surface of the pores. As the calcining temperature of the carbon material increases, the mesoporous structure of the carbon is destroyed. 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 10.5~15.5nm, 9~12nm and 7~9nm, respectively. This is basically consistent with the particle size obtained by XRD.
图4为实施例1的不同温度锻烧碳载体的催化剂的氮气吸脱附曲线。从图中可以看出：这三种不同的催化剂在相对压力P/P 0＝0.4～1之间均有一个回滞环，说明吸脱附曲线属于IV类等温吸附曲线，具有介孔结构，且煅烧温度更高的碳载体的回滞环更大，这可能是由于孔容变大的缘故。在回滞环的起始点B处，最小的孔内开始出现毛细管凝聚。随着相对压力P/P 0逐渐升高，中孔内也逐渐出现毛细管凝聚直到压力饱和，整个体系都被凝聚液填充满，出现了一个较大的回滞环。 4 shows the nitrogen adsorption and desorption curves of the catalyst calcined with carbon support at different temperatures in Example 1. FIG. It can be seen from the figure that these three different catalysts have a hysteresis loop between the relative pressure P/P 0 =0.4～1, indicating that the adsorption-desorption curve belongs to the IV type isotherm adsorption curve and has a mesoporous structure. Moreover, the hysteresis ring of the carbon support with higher calcination temperature is larger, which may be due to the larger pore volume. At the starting point B of the hysteresis loop, capillary condensation begins to appear in the smallest hole. As the relative pressure P/P 0 gradually increased, capillary condensation gradually appeared in the mesopores until the pressure was saturated. The entire system was filled with condensation liquid, and a larger hysteresis loop appeared.
图5为实施例1的不同温度锻烧碳载体的催化剂的孔径分布曲线。从图中可以看出：Co/GMC-700、Co/GMC-800和Co/GMC-900这三种催化剂的孔径基本都集中在3.9nm处。Fig. 5 is a pore size distribution curve of a catalyst calcined with a carbon support at different temperatures in Example 1. It can be seen from the figure that the pore diameters of the three catalysts Co/GMC-700, Co/GMC-800 and Co/GMC-900 are basically concentrated at 3.9nm.
表1为实施例1中Co/GMC-700、Co/GMC-800和Co/GMC-900的比表面积，孔径以及平均孔体积数据，从表中可以看出，催化剂Co/GMC-700、Co/GMC-800和Co/GMC-900的比表面积分别为207m 2.g -1、246m 2.g -1、306m 2.g -1；催化剂Co/GMC、Co/GMC-800和Co/GMC-900的平均孔体积分别为0.12cm 3.g -1、0.22cm 3.g -1、0.26cm 3.g -1。由上可知，随着碳载体锻烧温度的增加，催化剂的比表面积和总体积不断增大。 Table 1 shows the specific surface area, pore diameter and average pore volume data of Co/GMC-700, Co/GMC-800 and Co/GMC-900 in Example 1. It can be seen from the table that the catalysts Co/GMC-700, Co The specific surface areas of /GMC-800 and Co/GMC-900 are 207m 2 .g -1 , 246m 2 .g -1 , and 306m 2 .g -1 respectively ; the catalysts Co/GMC, Co/GMC-800 and Co/GMC an average pore volume of -900 respectively 0.12cm 3 .g -1, 0.22cm 3 .g -1, 0.26cm 3 .g -1. It can be seen from the above that as the calcination temperature of the carbon support increases, the specific surface area and total volume of the catalyst continue to increase.
表1实施例1中Co/GMC-700、Co/GMC-800和Co/GMC-900的比表面积，孔径以及平均孔体积数据Table 1 The specific surface area, pore diameter and average pore volume data of Co/GMC-700, Co/GMC-800 and Co/GMC-900 in Example 1
样品sample 比表面积(m 2.g -1) Specific surface area (m 2 .g -1 ) 孔径(nm)Aperture (nm) 平均孔径(cm 3.g -1) Average pore size (cm 3 .g -1 )
Co/GMC-700Co/GMC-700 207207 2.292.29 0.120.12
Co/GMC-800Co/GMC-800 246246 3.623.62 0.220.22
Co/GMC-900Co/GMC-900 306306 3.513.51 0.260.26
图6为实施例1的不同温度锻烧碳载体的催化剂的H 2-TPR图谱。从图中可以看出：所有催化剂均呈现三个氢的还原峰，其中从左至右第一个还原峰代表Co 3O 4→CoO的氢还原峰，而第二个代表CoO→Co的氢还原峰，第***碳载体的气化峰。此外，700℃以上再无还原峰，表明催化剂表面无难还原的化合物生成。锻烧温度更高的碳载体负载的钴基催化剂，实现Co 3O 4→CoO→Co活性相还原温度也更高，表明更高温度下煅烧出的碳载体，更有利于增加了介孔碳载体与钴之间的相互作用力的增强。TEM结合氮气物理吸附脱附BET分析表明：介孔碳材料介孔结构的塌陷引入了更多的物理缺陷，提高了钴在介孔碳载体上的分散能力，且钴粒径的变小增强了与载体间的相互作用力，提高了催化剂的稳定。 Fig. 6 shows the H 2 -TPR patterns of the catalyst calcined with a carbon support at different temperatures in Example 1. It can be seen from the figure that all catalysts show three reduction peaks of hydrogen. The first reduction peak from left to right represents the hydrogen reduction peak of Co 3 O 4 → CoO, and the second represents the hydrogen reduction peak of CoO → Co. Reduction peak, the third represents the gasification peak of the carbon carrier. In addition, there is no reduction peak above 700°C, indicating that no hard-to-reducible compounds are formed on the surface of the catalyst. The cobalt-based catalyst supported on a carbon support with a higher calcining temperature achieves a higher reduction temperature of the Co 3 O 4 →CoO→Co active phase, indicating that the carbon support calcined at a higher temperature is more conducive to increasing the mesoporous carbon The interaction between the carrier and the cobalt is enhanced. TEM combined with nitrogen physical adsorption and desorption BET analysis showed that the collapse of the mesoporous structure of the mesoporous carbon material introduced more physical defects, improved the dispersibility of cobalt on the mesoporous carbon support, and the reduction of the cobalt particle size increased The interaction force with the carrier improves the stability of the catalyst.
图7为实施例1的不同温度锻烧碳载体的催化剂在费托合成反应过程中CO转化率的变化。从图中可以看出：更高温度锻烧下的碳载体，CO转化率更高，结合TEM和氮气吸脱附BET分析，可能是由于温度升高介孔碳载体表面产生了更多的物理缺陷，并充分打开了介孔，增加了碳载体表面积，由于Co/GMC-800的比表面积相对于Co/GMC-700而言增长较小以及Co/GMC-800颗粒度较大的原因，导致800℃条件下煅烧成的Co/GMC-800催化剂的CO转化率相对较低。Co/GMC-700、Co/GMC-800和Co/GMC-900三种催化剂经过60h催化剂性能评价后，CO转化率分别由45％、37％和55％下降到35％、26％和42％。Fig. 7 shows the change in CO conversion rate of the catalyst calcined with carbon support at different temperatures in Example 1 during the Fischer-Tropsch synthesis reaction. It can be seen from the figure that the carbon support calcined at a higher temperature has a higher CO conversion rate. Combining TEM and nitrogen adsorption and desorption BET analysis, it may be due to the increase in temperature that the surface of the mesoporous carbon support produces more physical Defects, and fully opened the mesopores, and increased the surface area of the carbon support. The specific surface area of Co/GMC-800 has a smaller growth relative to Co/GMC-700 and the particle size of Co/GMC-800 is larger. The CO conversion rate of the Co/GMC-800 catalyst calcined at 800℃ is relatively low. After 60 hours of catalyst performance evaluation of Co/GMC-700, Co/GMC-800 and Co/GMC-900, the CO conversion rate decreased from 45%, 37% and 55% to 35%, 26% and 42% respectively .
表2为实施例1中Co/GMC-700、Co/GMC-800和Co/GMC-900催化剂的费托合成催化反应性能，从表中可以看出：Co/GMC-900的C 5+具有较高的选择性，这可能由于其石墨化程度较强及石墨缺陷促进了金属钴与CO之间的电子传递能力，进而活化CO分子，使得催化剂表面吸附的CO分子增多，有利于形成C 5+以上的混合物。 Table 2 shows the Fischer-Tropsch synthesis catalytic reaction performance of the Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts in Example 1. It can be seen from the table that the C 5+ of Co/GMC-900 has Higher selectivity, which may be due to its strong graphitization degree and graphite defects promote the electron transfer ability between the metal cobalt and CO, and then activate the CO molecules, so that the adsorbed CO molecules on the catalyst surface increase, which is beneficial to the formation of C 5 + A mixture of the above.
表2 实施例1中Co/GMC-700、Co/GMC-800和Co/GMC-900催化剂的费托合成催化反应性能Table 2 Fischer-Tropsch synthesis catalytic reaction performance of Co/GMC-700, Co/GMC-800 and Co/GMC-900 catalysts in Example 1
Figure PCTCN2020134712-appb-000006
Figure PCTCN2020134712-appb-000006
a反应条件:T＝270℃,P＝2MPa,H 2/CO＝2,GHSV＝3.6L·h -1g -1 a Reaction conditions: T=270℃, P=2MPa, H 2 / CO=2, GHSV=3.6L·h -1 g -1
b除二氧化碳外，碳氢化合物的选择性均已标准化。 b Except for carbon dioxide, the selectivity of hydrocarbons has been standardized.
c C ＝/C n是C 2-4的烯烃与石蜡的摩尔比。 c C = /C n is the molar ratio of C 2-4 olefin to paraffin.
图8为实施例1的不同温度锻烧碳载体的催化剂费托合成反应后的XRD。从图中可以看出：Co/GMC-700,Co/GMC-800和Co/GMC-900三个明显的衍射峰的2θ值为42.5°，45.7°和68.3°，对应于Co 2C(JCPDS 72-1369)的衍射特征峰，而另外的衍射峰Co 3C(JCPDS 89-2866)，分别对应于Co/GMC-700的60°，Co/GMC-800的60°和75°，Co/GMC-800的60°，75°和83°。另外，反应后催化剂Co/GMC-700，Co/GMC-800和Co/GMC-900都在2θ＝26.1°存在石墨化峰，但Co/GMC-900的最高。 FIG. 8 shows the XRD after the Fischer-Tropsch synthesis reaction of the catalyst calcined with carbon support at different temperatures in Example 1. FIG. It can be seen from the figure that the 2θ values of the three obvious diffraction peaks of Co/GMC-700, Co/GMC-800 and Co/GMC-900 are 42.5°, 45.7° and 68.3°, corresponding to Co 2 C(JCPDS 72-1369), while the other diffraction peaks of Co 3 C (JCPDS 89-2866) correspond to 60° of Co/GMC-700, 60° and 75° of Co/GMC-800, and Co/GMC-800. 60°, 75° and 83° of GMC-800. In addition, after the reaction, the catalysts Co/GMC-700, Co/GMC-800 and Co/GMC-900 all have graphitization peaks at 2θ=26.1°, but Co/GMC-900 has the highest graphitization peak.
图9为实施例1的不同温度锻烧碳载体的催化剂费托合成反应后透射电子显微镜照片，(a)为Co/GMC-700，(b)为Co/GMC-800，(c)Co/GMC-900。从图中可以看出：随着反应时间的变化，CoO颗粒粒径不断增大出现团聚现象；CoO的颗粒粒径分别为10.5～14nm，12.5～17.5nm和10～14nm。Fig. 9 is a transmission electron microscope photograph of the catalyst Fischer-Tropsch synthesis reaction of the carbon support calcined at different temperatures in Example 1, (a) is Co/GMC-700, (b) is Co/GMC-800, (c) Co/ GMC-900. It can be seen from the figure that as the reaction time changes, the particle size of CoO particles continues to increase and agglomeration occurs; the particle sizes of CoO particles are 10.5-14nm, 12.5-17.5nm and 10-14nm, respectively.
图10为实施例1的GMC-800和对照例1的CMK-3、AC的孔径分布图。从图中可以看出：GMC-800、CMK-3和AC的孔径分布主要集中于3.6nm、3.9nm和3.9nm，这说明用SBA-15为硬模板剂制备出的碳材料具有有序的介孔结构。FIG. 10 is a pore size distribution diagram of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1. FIG. It can be seen from the figure that the pore size distributions of GMC-800, CMK-3 and AC are mainly concentrated in 3.6nm, 3.9nm and 3.9nm, which shows that the carbon materials prepared with SBA-15 as the hard template have orderly Mesoporous structure.
图11为实施例1的GMC-800和对照例1的CMK-3的TEM图，(a)为GMC-800，(b)为CMK-3。从图中可以看出：所制备出来的GMC-800和CMK-3具有有序结构。Fig. 11 is a TEM image of GMC-800 of Example 1 and CMK-3 of Comparative Example 1, (a) is GMC-800, and (b) is CMK-3. It can be seen from the figure that the prepared GMC-800 and CMK-3 have an ordered structure.
图12为实施例1的GMC-800和对照例1的CMK-3、AC的氮气物理吸脱附曲线。从图中看出：在低区P/P 0(0～0.4)时，有很强的吸收峰，这是微孔的特征；在相对压力P/P 0＝0.4～1时，GMC-800和CMK-3都各有一回滞环，这说明它们的吸脱附曲线是典型的IV类曲线，具有典型的介孔结构。而AC的吸脱附曲线是I型等温线，为微孔结构。如图所示，催化剂的N 2吸附脱附等温线与其对应的载体吸附脱附等温线相似，这表明在制备过程中催化剂载体的结构性能变化较小。 Figure 12 shows the nitrogen physical adsorption and desorption curves of GMC-800 of Example 1 and CMK-3 and AC of Comparative Example 1. It can be seen from the figure that there is a strong absorption peak in the low zone P/P 0 (0～0.4), which is the characteristic of micropores; when the relative pressure P/P 0 ＝0.4～1, GMC-800 Both CMK-3 and CMK-3 have a hysteresis loop, which shows that their adsorption and desorption curves are typical class IV curves with typical mesoporous structure. The absorption and desorption curve of AC is an I-type isotherm, which is a microporous structure. As shown in the figure, the N 2 adsorption and desorption isotherm of the catalyst is similar to its corresponding support adsorption and desorption isotherm, which indicates that the structure and performance of the catalyst support change little during the preparation process.
图13为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC碳载体负载钴后的氮气物理吸附脱附等温曲线。从图中看出：CMK-3的比表面积、孔径和孔容在三种碳载体材料中都是最大的，分别为939m 2.g -1、1.31cm 3.g -1和5.57nm。AC和CMK-3的比表面积都高于GMC-800。对比载体的平均孔径，CMK-3的平均孔径最大(5.57nm)，AC最小(2.25nm)，GMC-800则居中(5.57nm)。另外，在相应碳载体上负载15wt.％钴元素后，载体的比表面积和孔体积显著下降。可能是由于钴的氧化颗粒填充于载体表面上的孔中所致。 Fig. 13 shows the nitrogen physical adsorption and desorption isotherms of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC carbon supports of Comparative Example 1 loaded with cobalt. It can be seen from the figure that the specific surface area, pore size and pore volume of CMK-3 are the largest among the three carbon support materials, which are respectively 939 m 2 .g -1 , 1.31 cm 3. G -1 and 5.57 nm. The specific surface area of AC and CMK-3 is higher than that of GMC-800. Comparing the average pore diameter of the carrier, the average pore diameter of CMK-3 is the largest (5.57nm), AC is the smallest (2.25nm), and GMC-800 is in the middle (5.57nm). In addition, after 15wt.% cobalt is loaded on the corresponding carbon support, the specific surface area and pore volume of the support significantly decrease. It may be due to the cobalt oxide particles filling the pores on the surface of the carrier.
表3为实施例1碳材料GMC-800和对照例1中的CMK-3、AC负载钴前后的物理化学性 质。从表中可以看出：CMK-3的比表面积、孔径和孔容在三种碳载体材料中都是最大的，分别为939m 2.g -1、1.31cm 3.g -1和5.57nm。AC和CMK-3的比表面积都高于GMC-800。对比载体的平均孔径，CMK-3的平均孔径最大(5.57nm)，AC最小(2.25nm)，GMC-800则居中(5.57nm)。另外，在相应碳载体上负载15wt.％钴元素后，载体的比表面积和孔体积显著下降。 Table 3 shows the physical and chemical properties of the carbon material GMC-800 in Example 1 and the CMK-3 and AC in Comparative Example 1 before and after loading cobalt. It can be seen from the table that the specific surface area, pore size and pore volume of CMK-3 are the largest among the three carbon support materials, which are respectively 939m 2 .g -1 , 1.31cm 3 .g -1 and 5.57nm. The specific surface area of AC and CMK-3 is higher than that of GMC-800. Comparing the average pore diameter of the carrier, the average pore diameter of CMK-3 is the largest (5.57nm), AC is the smallest (2.25nm), and GMC-800 is in the middle (5.57nm). In addition, after 15wt.% cobalt is loaded on the corresponding carbon support, the specific surface area and pore volume of the support significantly decrease.
表3为实施例1碳材料GMC-800和对照例1中的CMK-3、AC负载钴前后的物理化学性质Table 3 shows the physical and chemical properties of carbon material GMC-800 in Example 1 and CMK-3 and AC in Comparative Example 1 before and after loading cobalt
样品sample 比表面积(m 2.g -1) Specific surface area (m 2 .g -1 ) 孔径(nm)Aperture (nm) 平均孔径(cm 3.g -1) Average pore size (cm 3 .g -1 )
GMCGMC 442442 5.245.24 0.580.58
CMK-3CMK-3 939939 5.575.57 1.311.31
ACAC 657657 2.252.25 0.370.37
Co/GMC-800Co/GMC-800 246246 3.623.62 0.220.22
Co/CMK-3Co/CMK-3 709709 4.304.30 0.760.76
Co/ACCo/AC 492492 2.442.44 0.300.30
图14为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的XRD图。从图中看出：由于介孔材料的小角X射线衍射图谱主要在1～2处出现衍射峰，而所制备的催化剂Co/GMC-800和Co/CMK-3在1.039处出现衍射峰，这说明它们具有介孔结构。另外，由图可以看出：在2θ＝26.6°处的衍射峰对应石墨化碳的特征衍射峰，显示了多孔碳材料GMC的石墨化程度比CMK-3和AC高得多。而在2θ＝36.4°、42.3°、61.6°、73.9°和77.8°的衍射峰，说明催化剂中钴纳米颗粒主要以CoO(JCPDS 43-1004)的形式存在。比较图中不同催化剂的CoO特征衍射峰强度，发现催化剂Co/AC的CoO的峰强度强于催化剂Co/GMC-800和Co/CMK-3，说明催化剂Co/AC上的CoO颗粒更大。通过谢乐方程计算得到Co/GMC-800、Co/CMK-3和Co/AC催化剂CoO的平均粒径分别为11.6nm，6.9nm和19.2nm。14 is an XRD pattern of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG. It can be seen from the figure that the small-angle X-ray diffraction pattern of the mesoporous material mainly has diffraction peaks at 1 to 2, while the prepared catalysts Co/GMC-800 and Co/CMK-3 have diffraction peaks at 1.039. It shows that they have a mesoporous structure. In addition, it can be seen from the figure that the diffraction peak at 2θ=26.6° corresponds to the characteristic diffraction peak of graphitized carbon, which shows that the degree of graphitization of the porous carbon material GMC is much higher than that of CMK-3 and AC. The diffraction peaks at 2θ=36.4°, 42.3°, 61.6°, 73.9° and 77.8° indicate that the cobalt nanoparticles in the catalyst mainly exist in the form of CoO (JCPDS 43-1004). Comparing the CoO characteristic diffraction peak intensity of different catalysts in the figure, it is found that the CoO peak intensity of the catalyst Co/AC is stronger than that of the catalysts Co/GMC-800 and Co/CMK-3, indicating that the CoO particles on the catalyst Co/AC are larger. The average particle size of Co/GMC-800, Co/CMK-3 and Co/AC catalysts CoO calculated by Scherrer equation are 11.6nm, 6.9nm and 19.2nm, respectively.
图15为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的拉曼光谱。从图中看出：拉曼光图谱上有2个散射强度峰，前者是由单晶石墨缺陷引起的，被称为D峰，后者是由碳原子sp 2杂化的面内伸缩振动引起，被称为G峰。通常情况下，D峰与G峰的面积之比决定了碳材料的石墨化程度，I D/I G(两个峰的面积比)比值越小，则说明所制备出的碳材料石墨化程度越高。从图3.6中可看出，Co/GMC-800、Co/CMK-3、Co/AC的I D/I G的比值分别为1.94、1.98、2.65，这说明Co/GMC-800和Co/CMK-3的石墨化程度相对较高。 Figure 15 shows the Raman spectra of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. It can be seen from the figure that there are two scattering intensity peaks on the Raman spectrum. The former is caused by single-crystal graphite defects, called D peaks, and the latter is caused by the in-plane stretching vibration of the sp 2 hybridization of carbon atoms. , Is called G peak. Under normal circumstances, the ratio of the area of the D peak to the G peak determines the degree of graphitization of the carbon material. The smaller the ratio of I D /I G (the area ratio of the two peaks), the degree of graphitization of the prepared carbon material. Higher. It can be seen from Figure 3.6 that the I D /I G ratios of Co/GMC-800, Co/CMK-3, and Co/AC are 1.94, 1.98, and 2.65, respectively, which shows that Co/GMC-800 and Co/CMK -3 has a relatively high degree of graphitization.
图16为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的透射电子显微镜照片；(a)为Co/GMC-800，(b)为Co/CMK-3，(c)为Co/AC。从图中看出：催化剂Co/GMC-800和Co/CMK-3具有介孔结构。CoO颗粒均匀分散在介孔碳材料GMC上，且其结构较为规整； 而介孔碳材料CMK-3负载钴后，其有序介孔结构部分塌陷，但CoO纳米颗粒能均匀分散在CMK-3载体上。而对于Co/AC而言，CoO分散的相对集中。另外，通过TEM得出的粒径分布图，Co/GMC-800、Co/CMK-3、Co/AC中CoO的颗粒粒径分别为9～12nm，6.5～8nm和12～17.5nm。Figure 16 is a transmission electron micrograph 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. (c) is Co/AC. It can be seen from the figure that the catalysts Co/GMC-800 and Co/CMK-3 have a mesoporous structure. CoO particles are uniformly dispersed on the mesoporous carbon material GMC, and its structure is relatively regular; while the mesoporous carbon material CMK-3 is loaded with cobalt, its ordered mesoporous structure partially collapses, but the CoO nanoparticles can be uniformly dispersed in CMK-3 On the carrier. For Co/AC, CoO is relatively concentrated. 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 9-12nm, 6.5-8nm and 12-17.5nm, respectively.
图17为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的H 2-TPR图谱。从图中看出：所有催化剂均呈现三个氢的还原峰，其中从左至右第一个还原峰代表Co 3O 4→CoO的氢还原峰，而第二个还原峰代表CoO→Co的氢还原峰，第三个还原峰代表碳载体的气化峰。700℃以上再没有还原峰出现，表明催化剂表面上没有生成难还原的化合物，这也说明了钴氧化物与碳载体间的相互作用力要比氧化物载体(例如：SiO 2和Al 2O 3)与钴催化剂之间的相互作用力弱的多。 FIG. 17 shows the H 2 -TPR patterns of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG. It can be seen from the figure that all catalysts show three reduction peaks of hydrogen. The first reduction peak from left to right represents the hydrogen reduction peak of Co 3 O 4 → CoO, and the second reduction peak represents the reduction peak of CoO → Co. The hydrogen reduction peak, the third reduction peak represents the gasification peak of the carbon carrier. There is no reduction peak above 700℃, indicating that no hard-to-reducible compounds are formed on the surface of the catalyst. This also shows that the interaction force between cobalt oxide and carbon support is better than that of oxide support (for example: SiO 2 and Al 2 O 3 The interaction force between) and the cobalt catalyst is much weaker.
图18为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC在费托合成反应过程中CO转化率的变化。从图中看出：由于受载体结构性能的影响，三种催化剂的稳定性表现不一。催化剂Co/CMK-3的催化活性较为稳定，催化反应进行60h后，CO的转化率由21％下降15％，而Co/GMC的CO转化率由37％下降到26％,Co/AC的CO转化率由19％下降9％。Figure 18 shows the changes in the CO conversion rate of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 during the Fischer-Tropsch synthesis reaction. It can be seen from the figure that the stability of the three catalysts is different due to the influence of the structural properties of the support. The catalytic activity of the catalyst Co/CMK-3 is relatively stable. After the catalytic reaction is carried out for 60 hours, the CO conversion rate has dropped from 21% by 15%, while the CO conversion rate of Co/GMC has dropped from 37% to 26%. The CO conversion rate of Co/AC The conversion rate decreased by 9% from 19%.
表4为实施例1的Co/GMC-800和对照例1的Co/CMK-3、Co/AC催化剂的费托合成催化反应性能。从表中可以看出：Co/GMC-800具有较高的Conv. CO(29.4％)，这可能由于GMC-800石墨化程度较高，利于钴与CO间电子转移，进而促进CO活化。而Co/CMK-3催化剂虽然具有较大的比表面积和孔容，但Conv. CO只有18.05％，可能是由于负载钴后CMK-3呈无定形性、较差的石墨化结构及制备过程中部分有序结构破坏造成的。另外，从表中可以看出：高的C 5+选择性往往伴随着低的CH 4和C 2-C 4选择性，催化剂Co/GMC-800相比于催化剂Co/CMK-3和Co/AC可获得更多C 5+烃类产物和较低的甲烷和C 2-C 4。这可能是由于其石墨化程度较强促进了金属钴与CO之间的电子传递能力，进而活化CO分子，使得催化剂表面吸附的CO分子增多，有利于形成C 5+以上的混合物。 Table 4 shows the Fischer-Tropsch synthesis catalytic reaction performance of the Co/GMC-800 of Example 1 and the Co/CMK-3 and Co/AC catalysts of Comparative Example 1. It can be seen from the table that Co/GMC-800 has a higher Conv. CO (29.4%), which may be due to the higher degree of graphitization of GMC-800, which facilitates the transfer of electrons between cobalt and CO and promotes CO activation. Although the Co/CMK-3 catalyst has a larger specific surface area and pore volume, the Conv. CO is only 18.05%, which may be due to the amorphous and poor graphitized structure of CMK-3 after cobalt loading. Caused by the destruction of part of the orderly structure. In addition, it can be seen from the table that high C 5+ selectivity is often accompanied by low CH 4 and C 2 -C 4 selectivity. The catalyst Co/GMC-800 is compared with the catalyst Co/CMK-3 and Co/ AC can obtain more C 5+ hydrocarbon products and lower methane and C 2 -C 4 . This may be due to the strong graphitization degree which promotes the electron transfer ability between the metal cobalt and CO, and then activates the CO molecules, which makes the CO molecules adsorbed on the catalyst surface increase, which is conducive to the formation of a mixture of C 5+ and above.
表4实施例1的Co/GMC-800和对照例1的Co/CMK-3、Co/AC催化剂的费托合成催化反应性能Table 4 Fischer-Tropsch synthesis catalytic reaction performance of Co/GMC-800 in Example 1 and Co/CMK-3 and Co/AC catalysts in Comparative Example 1
Figure PCTCN2020134712-appb-000007
Figure PCTCN2020134712-appb-000007
a反应条件:T＝270℃,P＝2MPa,H 2/CO＝2,GHSV＝3.6L·h -1g -1 a Reaction conditions: T=270℃, P=2MPa, H 2 / CO=2, GHSV=3.6L·h -1 g -1
b除二氧化碳外，碳氢化合物的选择性均已标准化。 b Except for carbon dioxide, the selectivity of hydrocarbons has been standardized.
c C ＝/C n是C 2-4的烯烃与石蜡的摩尔比。 c C = /C n is the molar ratio of C 2-4 olefin to paraffin.
图19为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的费托合成反应后的XRD。从图中看出：Co/GMC和Co/CMK-3三个明显的衍射峰的2θ值为42.5°，45.7°和68.3°，对应于Co 2C(JCPDS 72-1369)的衍射特征峰，而另外两个的衍射峰对应于Co 3C(JCPDS89-2866)，其2θ值为60°和75°。这说明了反应后催化剂有新的物种出现，这也是导致反应过程一氧化碳随时间下降的一个主要原因。另外，反应后催化剂Co/GMC和Co/CMK-3在2θ＝26.1°的石墨化衍射峰明显增强。 FIG. 19 shows the XRD after the Fischer-Tropsch synthesis reaction of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1. FIG. It can be seen from the figure that the 2θ values of the three obvious diffraction peaks of Co/GMC and Co/CMK-3 are 42.5°, 45.7° and 68.3°, which correspond to the characteristic diffraction peaks of Co 2 C (JCPDS 72-1369). The other two diffraction peaks correspond to Co 3 C (JCPDS89-2866), and their 2θ values are 60° and 75°. This shows that new species appear in the catalyst after the reaction, which is also a main reason for the decrease of carbon monoxide over time in the reaction process. In addition, the graphitization diffraction peaks of the catalysts Co/GMC and Co/CMK-3 at 2θ=26.1° were significantly enhanced after the reaction.
图20为实施例1的Co/GMC-800和对照例1的Co/CMK-3和Co/AC的费托合成反应后的透射电子显微镜照片。从图中看出：随着反应时间的变化，CoO颗粒粒径不断增大出现团聚现象。通过TEM得出的粒径分布图，Co/GMC-800、Co/CMK-3、Co/AC中CoO的颗粒粒径分别为12.5～17.5nm，12～17nm和15～25nm。由此也证实了掺杂氮后催化剂CO转化率下降较快的原因。20 is a transmission electron microscope photograph of Co/GMC-800 of Example 1 and Co/CMK-3 and Co/AC of Comparative Example 1 after the Fischer-Tropsch synthesis reaction. It can be seen from the figure that as the reaction time changes, the particle size of CoO particles increases continuously and agglomerates. 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 12.5 to 17.5 nm, 12 to 17 nm and 15 to 25 nm, respectively. This also confirmed the reason why the CO conversion rate of the catalyst decreased rapidly after doping with nitrogen.
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed as above in preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention should be defined by the claims.

Claims (10)

  1. 一种介孔碳材料的制备方法，其特征在于，包括以下步骤：A preparation method of mesoporous carbon material, characterized in that it comprises the following steps:
    S1：采用固-液球磨模板法将SBA-15与大豆油混合均匀；S1: Use solid-liquid ball mill template method to mix SBA-15 and soybean oil evenly;
    S2：将S1的混合物转入石英管式炉中，升温至700-900℃碳化；S2: Transfer the mixture of S1 into a quartz tube furnace and heat up to 700-900°C for carbonization;
    S3：将S2的混合物用NaOH溶液刻蚀，即可得到所述的介孔碳材料。S3: The mixture of S2 is etched with NaOH solution to obtain the mesoporous carbon material.
  2. 根据权利要求1所述的制备方法，其特征在于，S1所述的SBA-15与大豆油混合物的质量比为1:2。The preparation method according to claim 1, wherein the mass ratio of the SBA-15 and soybean oil mixture of S1 is 1:2.
  3. 根据权利要求1所述的制备方法，其特征在于，S2所述的碳化过程具体为：在N 2保护下，升温速率为：4℃·min -1，碳化时间为5h。 The preparation method according to claim 1, wherein the carbonization process of S2 is specifically: under N 2 protection, a heating rate of 4° C.·min -1 , and a carbonization time of 5 h.
  4. 权利要求1的制备方法得到的介孔碳材料。The mesoporous carbon material obtained by the preparation method of claim 1.
  5. 一种包含权利要求1所述的介孔碳材料负载的钴基催化剂。A cobalt-based catalyst comprising the mesoporous carbon material supported by claim 1.
  6. 权利要求5所述的催化剂的制备方法，其特征在于，包括以下步骤：The preparation method of the catalyst according to claim 5, characterized in that it comprises the following steps:
    (1)将Co(NO 3) 2·6H 2O溶于无水乙醇溶液中； (1) Dissolve Co(NO 3 ) 2 ·6H 2 O in anhydrous ethanol solution;
    (2)将介孔碳材料浸入步骤(1)的溶液中，然后在旋转蒸发仪中蒸发，得到混合物；(2) Immerse the mesoporous carbon material in the solution of step (1), and then evaporate in a rotary evaporator to obtain a mixture;
    (3)将步骤(2)的混合物放入烘箱中干燥；然后煅烧，即可以得到所述的催化剂。(3) Put the mixture of step (2) into an oven to dry; then calcinate, and then the catalyst can be obtained.
  7. 根据权利要求6所述的制备方法，其特征在于，步骤(1)所述的Co(NO 3) 2·6H 2O和无水乙醇的质量比为1：5-50。 The preparation method according to claim 6, wherein the mass ratio of Co(NO 3 ) 2 ·6H 2 O and absolute ethanol in step (1) is 1:5-50.
  8. 根据权利要求6所述的制备方法，其特征在于，步骤(3)所述的煅烧具体为：在N 2氛围下煅烧350℃，升温速率为3℃·min -1，煅烧时间为2-10h。 The preparation method according to claim 6, wherein the calcination in step (3) is specifically: calcination at 350°C under N 2 atmosphere, a heating rate of 3°C·min -1 , and a calcination time of 2-10h .
  9. 权利要求4所述的介孔碳材料在催化、电化学、环境或磁催化领域中的应用。The application of the mesoporous carbon material of claim 4 in the fields of catalysis, electrochemistry, environment or magnetocatalysis.
  10. 权利要求5所述的介孔碳材料负载的钴基催化剂在工业制氢中的应用。The application of the cobalt-based catalyst supported by the mesoporous carbon material of claim 5 in industrial hydrogen production.
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