CN115400780A - KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof - Google Patents
KOH activated nitrogen-doped carbon material supported catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/617—
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- B01J35/618—
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- B01J35/633—
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- B01J35/635—
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- B01J35/643—
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- 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
Abstract
The application discloses KOH activation nitrogen-doped carbon material supported catalyst and preparation method, KOH activation nitrogen-doped carbon material supported catalyst includes carrier and metal active component, the carrier includes KOH activation nitrogen-doped carbon material. The KOH activated nitrogen-doped carbon material supported catalyst effectively improves the specific surface area and the nitrogen doping degree of a carrier, and changes the percentage of different nitrogen species, so that the carbon-nitrogen configuration is changed, the generation of pyrrole nitrogen is promoted, more electron-rich sites are exposed, the electron cloud density of Fe is improved, the CO dissociation and the generation of active components are promoted, and the reaction activity is remarkably improved; effectively improves the proportion of low-carbon olefin in the product, is beneficial to the directional production of the low-carbon olefin, and adopts the activated carbon and SiO (2-4) value 2 And gamma-Al 2 O 3 As carriersThe traditional catalyst is respectively improved by 0.40, 1.63 and 1.33 times.
Description
Technical Field
The application belongs to the technical field of catalytic conversion of synthesis gas, and particularly relates to a KOH activated nitrogen-doped carbon material supported catalyst and a preparation method thereof.
Background
Synthesis gas is an important chemical raw material gas, and can be used for preparing various hydrocarbon chemicals, including long-carbon hydrocarbons (such as gasoline, kerosene, diesel oil and wax) and short-carbon hydrocarbons (such as ethylene, propylene and butylene). The synthesis gas has wide sources and can be obtained by converting coal, petroleum, natural gas, biomass and the like. In consideration of the current situations of abundant coal resources and high external dependence of crude oil in China, the development of a chemical route for efficiently utilizing the coal-based synthesis gas has important strategic significance for stabilizing national energy safety and promoting energy diversification.
Fischer-Tropsch synthesis is the synthesis of synthesis gas (CO and H) 2 ) Converted to clean liquid fuels or other hydrocarbon chemicals over a catalyst. Specifically, the reaction process comprises the steps of dissociating CO on the surface of the metal catalyst, coupling carbon with carbon, hydrogenating and the like, and finally, a mixture of alkane, alkene and the like is generated. The products of the current industrial Fischer-Tropsch synthesis process are mainly concentrated on oil products and low-carbon olefins (C) 2 -C 4 =), the commonly used catalyst comprises metals such as Fe, co and the like, wherein the Fe-based catalyst is often used in the reaction field of preparing low-carbon olefin from synthesis gas due to wide process operation range and weak carbon chain growth capability.
At present, the carrier of the Fischer-Tropsch synthesis Fe-based catalyst is oxide (such as SiO) 2 、Al 2 O 3 Etc.), but the interaction force between the metal and the carrier is strong, so that the metal is difficult to be reduced and carbonized further to generate an active phase state, and the activity of the catalyst is influenced.
Disclosure of Invention
The application aims to provide a KOH activated nitrogen-doped carbon material supported catalyst and a preparation method thereof, and the catalyst and the preparation method thereof are used for solving the technical problem that in the prior art, the carrier of a Fischer-Tropsch synthesis Fe-based catalyst is mainly oxide, but the interaction force between metal and the carrier is strong, so that the metal is difficult to be reduced and further carbonized to generate an active phase state, and the activity of the catalyst is influenced.
In order to achieve the above purpose, the present application adopts a technical solution that: a KOH-activated nitrogen-doped carbon material supported catalyst is provided, comprising a support comprising a KOH-activated nitrogen-doped carbon material and a metal active component.
In one or more embodiments, the metal active component is one or a combination of more of Fe, co, and Ni.
In one or more embodiments, the KOH-activated nitrogen-doped carbon material has a residual K element content of 0 to 1.8%.
Preferably, the content of K element remaining in the KOH-activated nitrogen-doped carbon material is 0.6%.
In one or more embodiments, the nitrogen-doped carbon material is an organo-metallic framework ZIF-8 derived nitrogen-doped carbon material.
In order to achieve the above purpose, the present application adopts another technical solution: the preparation method of the KOH activated nitrogen-doped carbon material supported catalyst comprises the following steps:
preparing a nitrogen-doped carbon material;
uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating and drying, activating and roasting in an inert gas atmosphere, and washing to obtain a KOH-activated nitrogen-doped carbon material;
and (3) dipping the metal active component solution into the nitrogen-doped carbon material activated by the KOH, uniformly dispersing, drying and roasting to obtain the catalyst.
In one or more embodiments, the step of preparing the nitrogen-doped carbon material specifically includes:
dissolving metal zinc salt and nitrogen-containing organic ligand in deionized water, and stirring to obtain white solid precipitate;
and washing and drying the white solid precipitate, and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
In one or more embodiments, the metal zinc salt is zinc nitrate hexahydrate, the nitrogen-containing organic ligand is 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to deionized water is 0.11 (0.33-0.40) (60-70), and in the step of washing and drying the white solid precipitate, and then roasting the white solid precipitate in an inert gas atmosphere to obtain the nitrogen-doped carbon material, the roasting temperature is 900-1100 ℃.
In one or more embodiments, in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, and washing to obtain a KOH-activated nitrogen-doped carbon material,
the mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material is (1-3) to 1, the temperature of the activation roasting is 600-800 ℃, and the time of the activation roasting is 1-3 h.
In one or more embodiments, in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating and roasting in an inert gas atmosphere, and washing to obtain a KOH-activated nitrogen-doped carbon material,
the washing is specifically that firstly dilute hydrochloric acid is adopted for washing, and then deionized water is used for washing until the pH value is =7, so as to completely remove KOH; or directly washing with deionized water to ensure that the content of the residual K element is 0.6 to 1.8 percent.
Preferably, the washing is specifically direct washing with deionized water, so that the content of the residual K element is 0.6%.
In one or more embodiments, in the step of immersing the metal active component solution into the nitrogen-doped carbon material activated by KOH, dispersing uniformly, drying, and calcining to obtain the final product,
the metal active component solution comprises one or more of Fe, co and Ni ion solutions, the drying temperature is 50-80 ℃, the drying time is 8-24 hours, the roasting temperature is 400-600 ℃, and the roasting time is 2-4 hours.
In order to achieve the above object, the present application adopts another technical solution: the KOH-activated nitrogen-doped carbon material supported catalyst according to any one of the embodiments is applied to the promotion of the conversion rate of synthesis gas and the improvement of the low-carbon olefin ratio in a product in a Fischer-Tropsch synthesis reaction.
Different from the prior art, the beneficial effects of this application are:
the KOH activated nitrogen-doped carbon material supported catalyst adopts a KOH activated nitrogen-doped carbon material as a carrier, so that the specific surface area and the nitrogen doping degree of the carrier are effectively improved, the percentage of different types of nitrogen is changed, the carbon-nitrogen configuration is changed, the generation of pyrrole nitrogen is promoted, more electron-rich sites are exposed, the electron cloud density of Fe is improved, the CO dissociation and the generation of active components are promoted, and the reaction activity is remarkably improved; compared with the method adopting active carbon and SiO 2 And gamma-Al 2 O 3 The conversion rate of CO in the conversion reaction process of the synthetic gas is respectively improved by 9.96 times, 5.30 times and 3.49 times by using the traditional catalyst as the carrier.
This application KOH activation nitrogen-doped carbon material supported catalyst adopts the nitrogen-doped carbon material of KOH activation as the carrier, for not having the nitrogen-doped carbon material through KOH activation as the carrier, catalytic activity has shown the improvement, when synthetic gas conversion reaction 15h, the CO conversion rate has promoted 84%.
The KOH activated nitrogen-doped carbon material supported catalyst effectively improves the proportion of low-carbon olefin in the product, is beneficial to directionally producing the low-carbon olefin, and has an O/P (2-4) value relative to that of activated carbon and SiO 2 And gamma-Al 2 O 3 The traditional catalyst used as the carrier is improved by 0.40, 1.63 and 1.33 times respectively.
The preparation method of the KOH activated nitrogen-doped carbon material supported catalyst can realize different K element residual contents in the KOH activated nitrogen-doped carbon material through different washing means, and the residual K element can further promote adsorption and dissociation of CO, so that the reaction activity is further improved.
Drawings
FIG. 1 is a transmission electron micrograph and a particle size distribution graph of effect example 1;
fig. 2 is a graph showing the change in CO conversion rate during the synthesis gas conversion reaction of example 5 and comparative example 2 in effect example 3.
Detailed Description
At present, the carrier of the catalyst for Fischer-Tropsch synthesis is SiO 2 、Al 2 O 3 The oxides are main, and the interaction force between the carrier oxide and the metal is strong, so that the metal is difficult to reduce and further carbonize to generate an active phase state, and the activity of the catalyst is correspondingly influenced.
To solve this problem, the applicant developed a catalyst using nitrogen-doped carbon material activated with KOH as a support to avoid the problems of the conventional support.
Specifically, referring to fig. 1, fig. 1 is a preparation method of a KOH activated nitrogen-doped carbon material supported catalyst, which includes:
s100, preparing the nitrogen-doped carbon material.
In one embodiment, the nitrogen-doped carbon material is a nitrogen-doped carbon material derived from the organic metal framework ZIF-8, and the organic metal framework ZIF-8 has the advantages of porosity, high chemical stability and thermal stability, low cost, easiness in obtaining and the like, and is beneficial to improving the loading rate and catalytic activity of the catalyst.
Specifically, referring to fig. 2, fig. 2 is a schematic flowchart illustrating an embodiment corresponding to step S100 in fig. 1.
The step of preparing the nitrogen-doped carbon material comprises the following steps:
s101, dissolving metal zinc salt and a nitrogen-containing organic ligand in deionized water, and stirring to obtain a white solid precipitate.
And S102, washing and drying the white solid precipitate, and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
The metal zinc salt can be zinc nitrate hexahydrate, the nitrogen-containing organic ligand can be 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to the deionized water can be 0.11 (0.33-0.40) to (60-70), and the roasting temperature can be 900-1100 ℃.
The nitrogen-doped carbon material with the organic metal framework ZIF-8 derived can be obtained by stirring, mixing and precipitating zinc nitrate hexahydrate and 2-methylimidazole at room temperature, and then roasting in an inert gas atmosphere.
In the present embodiment, the room temperature is 25. + -. 5 ℃. In other embodiments, the nitrogen-doped carbon material may also be a nitrogen-doped carbon material with other configurations and prepared by other preparation methods, and the effects of the embodiments can be achieved.
And S200, uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating, drying, activating, roasting in an inert gas atmosphere, and washing to obtain the KOH-activated nitrogen-doped carbon material.
The nitrogen-doped carbon material is dispersed in KOH, evaporated, dried and then roasted, so that the nitrogen-doped carbon material can be effectively activated, the specific surface area and the nitrogen doping degree of the nitrogen-doped carbon material are improved, the percentage of different nitrogen species is changed, the carbon-nitrogen configuration is changed, the generation of pyrrole nitrogen is promoted, and more electron-rich sites are exposed.
More electron-rich sites are introduced, so that the CO dissociation and metal carbonization processes in the Fischer-Tropsch synthesis reaction are facilitated, and the activity of the catalyst is improved.
The mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material can be (1-3) to 1; the temperature of the activation roasting can be 600-800 ℃, the time of the activation roasting can be 1-3 h, and the nitrogen-doped carbon material can have rich pore structures and proper nitrogen configuration.
When the temperature of the activation roasting is gradually increased from 600 ℃ to 800 ℃, more carbon reacts in KOH, so that more pore structures are generated, and the specific surface area of the corresponding nitrogen-doped carbon material is gradually increased.
With the temperature of the activation roasting increasing, the carbon-nitrogen configuration changes gradually, and when the temperature of the activation roasting is 700 ℃, the generated KOH-activated nitrogen-doped carbon material has the optimal configuration and can expose the most electron-rich sites.
The wash may be a dilute hydrochloric acid wash followed by a deionized water wash to pH =7 to completely remove KOH.
The washing can also be directly washed by deionized water, so that part of KOH remains on the nitrogen-doped carbon material, the content of the residual K element is controlled to be 0.6-1.8%, and the content of the residual K element is preferably 0.6%.
The proper residual K can further promote the adsorption and dissociation of CO and improve the catalytic performance; however, when the content of the residual K element is too high, the carbon deposition may be serious, resulting in a decrease in the catalyst activity.
S300, dipping the metal active component solution into the nitrogen-doped carbon material activated by KOH, uniformly dispersing, drying and roasting to obtain the catalyst.
The metal active component solution may be one or a combination of Fe, co and Ni ion solutions. By dipping the metal active component solution on the nitrogen-doped carbon material activated by KOH, drying and roasting, the metal active component can be effectively loaded in the pore structure of the nitrogen-doped carbon material.
Due to the high specific surface area, multiple electron-rich sites and weak interaction force between the nitrogen-doped carbon material activated by KOH and metal, the metal can participate in the reaction more efficiently in the Fischer-Tropsch synthesis reaction, so that the adsorption and dissociation of CO are promoted, and the catalytic performance is improved.
The application also provides a KOH-activated nitrogen-doped carbon material supported catalyst prepared by adopting any one of the above embodiments, which comprises a carrier and metal active components, wherein the carrier comprises a KOH-activated nitrogen-doped carbon material, the metal active components are one or more of Fe, co and Ni, and the weight ratio of the carrier to the metal active components is (80-95): (5-20), the content of the residual K element in the nitrogen-doped carbon material activated by KOH is 0-1.8%.
The present application will be described in detail with reference to various embodiments. The embodiments are not intended to limit the present application, and structural, methodological, or functional changes made by those skilled in the art according to the embodiments are included in the scope of the present application.
In the following examples and effect examples, the TEM of a sample was measured by using a Japanese JEM-2100F TEM; specific surface area and pore structure parameters of the samples were measured by a Micromeritics company ASAP2460 physisorption instrument, usa; the K element content of the sample is analyzed by an inductively coupled plasma emission spectrometer (model Vista-MPX) of Varian corporation in America.
Example 1:
a KOH activated nitrogen doped carbon material supported catalyst is prepared by the following steps:
(1) 0.33gZn (NO) 3 ) 2 ·6H 2 Dissolving O and 0.99g of 2-methylimidazole in 90mL of deionized water respectively, then uniformly mixing the two solutions, magnetically stirring for 24 hours at room temperature, centrifugally separating, washing, and drying for 12 hours at 50 ℃ to obtain white solid powder, namely the metal organic framework ZIF-8;
(2) Calcining white solid powder under inert gas Ar at 1000 deg.C for 2 deg.C/min -1 Heating to the target temperature at the rate of (2) and keeping the flow rate of Ar at 120 mL/min -1 Obtaining nitrogen-doped carbon material;
(3) Mixing 0.72g of nitrogen-doped carbon material and 1.44g of KOH, dispersing the mixture in 30mL of deionized water, uniformly stirring the mixture, putting the mixture into an oil bath kettle at 80 ℃, stirring the mixture to evaporate water until the mixture becomes smooth viscous liquid, drying the viscous liquid in vacuum at 80 ℃ for 12 hours, activating and roasting the viscous liquid in inert gas Ar at the activation roasting temperature of 600 ℃, and setting the activation roasting temperature at 1 ℃ for min -1 Heating to the target temperature at the rate of (1) and keeping the flow rate of Ar at 1h -1 (ii) a Fully grinding the sample after activation roasting, adding 250mL of 1mol/L diluted hydrochloric acid, uniformly mixing, stirring for 4 hours in a water bath at 80 ℃, washing to be neutral by using deionized water, and drying to obtain a KOH activated nitrogen-doped carbon material;
(4) Weighing 0.214g of ferric ammonium citrate, dissolving the ferric ammonium citrate in 1mL of deionized water, dropwise adding a ferric citrate aqueous solution into the prepared KOH-activated nitrogen-doped carbon material, then carrying out ultrasonic treatment for 30min, carrying out vacuum drying on the immersed sample at 50 ℃ for 12h, and roasting the immersed sample in a tubular furnace at the heating rate of 5 ℃/min at 500 ℃ for 2h in an inert gas Ar atmosphere; after the roasting is finished and the temperature is reduced to the room temperature, 1%O is pumped into the tubular furnace 2 Passivating the/Ar mixed gas for 1 hour to obtain。
Example 2:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 1, except that:
the temperature for activation baking in step (3) of this example was 700 ℃.
Example 3:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 1, except that:
the temperature of the activation baking in step (3) of this example was 750 ℃.
Example 4:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 1, except that:
the temperature of the activation baking in step (3) of this example was 800 ℃.
Example 5:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 2, except that:
in the step (3) of this embodiment, the sample after activation baking is fully ground, and then is directly washed with deionized water, where the usage amount of deionized water is 3L, so that a K element content with a mass fraction of 0.6% remains in the KOH activated nitrogen-doped carbon material.
Example 6:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 2, except that:
in the step (3) of this embodiment, after the sample after activation baking is fully ground, the sample is directly washed with deionized water, and the amount of the deionized water is 2L, so that the content of K element with a mass fraction of 1.1% remains in the KOH-activated nitrogen-doped carbon material.
Example 7:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 4, except that:
in the step (3) of this embodiment, after the sample after activation baking is fully ground, the sample is directly washed with deionized water, and the amount of the deionized water is 1L, so that the content of K element with a mass fraction of 1.8% remains in the KOH-activated nitrogen-doped carbon material.
Example 8:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 1, except that:
in this example, 0.127g of nickel nitrate was dissolved in 1ml of deionized water instead of 0.214g of ammonium iron citrate in step (4).
Example 9:
a KOH-activated nitrogen-doped carbon material supported catalyst prepared substantially as in example 1, except that:
in this example, in step (4), 0.128g of cobalt nitrate hexahydrate was dissolved in 1ml of deionized water in place of 0.214g of ammonium iron citrate.
Comparative example 1:
a catalyst, the method of preparation comprising:
weighing 0.214g of ferric ammonium citrate, dissolving the ferric ammonium citrate in 1mL of deionized water, dropwise adding a ferric citrate aqueous solution onto activated carbon, then carrying out ultrasonic treatment for 30min, carrying out vacuum drying on the immersed sample at 50 ℃ for 12h, and roasting the immersed sample in a tubular furnace at 500 ℃ for 2h at a heating rate of 5 ℃/min, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and the temperature is reduced to the room temperature, 1%O is pumped into the tubular furnace 2 Passivating the/Ar mixed gas for 1 hour to obtain the catalyst.
Among them, activated carbon is commercially available activated carbon provided by fujian xin sen carbon limited.
Comparative example 2:
a catalyst, the preparation method comprising:
(1) 0.33gZn (NO) 3 ) 2 ·6H 2 Dissolving O and 0.99g of 2-methylimidazole in 90mL of deionized water respectively, then uniformly mixing the two solutions, magnetically stirring for 24 hours at room temperature, centrifugally separating, washing, and drying for 12 hours at 50 ℃ to obtain white solid powder, namely the metal organic framework ZIF-8;
(2) Mixing white solid powder withRoasting under inert gas Ar at 1000 deg.C for 2 deg.C/min -1 Heating to the target temperature at the rate of (2) and keeping the flow rate of Ar at 120 mL/min -1 Obtaining nitrogen-doped carbon material;
(3) Weighing 0.214g of ferric ammonium citrate, dissolving the ferric ammonium citrate in 1mL of deionized water, dropwise adding a ferric citrate aqueous solution onto a nitrogen-doped carbon material, then carrying out ultrasonic treatment for 30min, carrying out vacuum drying on the immersed sample at 50 ℃ for 12h, and roasting the immersed sample in a tubular furnace at 500 ℃ for 2h at a heating rate of 5 ℃/min, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and the temperature is reduced to the room temperature, 1%O is pumped into the tubular furnace 2 Passivating the/Ar mixed gas for 1 hour to obtain the catalyst.
Comparative example 3:
a catalyst, the method of preparation comprising:
weighing 0.214g of ferric ammonium citrate, dissolving the ferric ammonium citrate in 1mL of deionized water, dropwise adding a ferric citrate aqueous solution onto silicon dioxide, then carrying out ultrasonic treatment for 30min, carrying out vacuum drying on the soaked sample at 50 ℃ for 12h, and roasting the sample in a tubular furnace at 500 ℃ for 2h at a heating rate of 5 ℃/min, wherein the roasting atmosphere is inert gas Ar; after the roasting is finished and the temperature is reduced to the room temperature, 1%O is pumped into the tubular furnace 2 Passivating the/Ar mixed gas for 1 hour to obtain the catalyst.
Comparative example 4:
a catalyst, the method of preparation comprising:
0.214g ferric ammonium citrate is weighed and dissolved in 1mL deionized water, and the ferric citrate aqueous solution is added dropwise to the gamma-Al 2 O 3 Carrying out ultrasonic treatment for 30min, carrying out vacuum drying on the immersed sample at 50 ℃ for 12h, and roasting the immersed sample in a tube furnace at a heating rate of 5 ℃/min at 500 ℃ for 2h in an inert gas Ar atmosphere; after the roasting is finished and the temperature is reduced to the room temperature, 1%O is pumped into the tubular furnace 2 Passivating the/Ar mixed gas for 1 hour to obtain the catalyst.
Effect example 1: characterization of catalyst
Transmission electron microscopy analysis was performed on the KOH-activated nitrogen-doped carbon material supported catalysts prepared in examples 1 to 4 to obtain a transmission electron microscopy image and a particle size distribution curve as shown in fig. 1, wherein a, b, c, d correspond to examples 1, 2, 3, 4, respectively.
As shown in fig. 1, in the catalysts prepared in examples 1 to 4, fe nanoparticles were small in size and uniformly dispersed, and the average particle diameters thereof were 5.0nm, 4.7nm, 4.6nm, and 4.9nm, respectively. Therefore, the catalysts prepared in examples 1 to 4 can uniformly load small-particle-size metal nanoparticles, and are helpful for improving the catalytic performance in the Fischer-Tropsch synthesis.
Effect example 2: vector characterization assay
The specific surface area and pore structure parameters of the KOH-activated nitrogen-doped carbon materials prepared in examples 1 through 4 were measured to obtain the data in the following table.
As can be seen from the above table, as the activation baking temperature of KOH activation increases, the specific surface area and pore volume of the obtained KOH-activated nitrogen-doped carbon material gradually increase, while the average pore diameter remains small.
This is mainly due to the fact that when the temperature of the activation firing is gradually increased from 600 ℃ to 800 ℃, more carbon is reacted with KOH, so that more pore structures are generated, and the specific surface area of the corresponding nitrogen-doped carbon material is gradually increased.
Effect example 3: analysis of catalytic Properties
The catalysts prepared in examples 1 to 9 and comparative examples 1 to 4 were taken, tableted and sieved to 40 to 60 mesh, respectively, 0.1g of the catalyst was taken and mixed with 1.9g of quartz sand, and the evaluation of the catalyst reaction was carried out in a pressurized micro-reaction system.
Specifically, at 340 ℃ and 1.0MPa, reaction gases CO, H2 and an internal standard gas Ar are introduced, the feeding flow rate ratio of CO/H2/Ar =4.5/4.5/1.0 is ensured, and the ratio (space velocity) of the flow rate of the reaction gases to the amount of the catalyst is 9000mL g -1 ·h -1 The reaction is carried out. Before reaction, the catalyst is in-situ high-purity H 2 Reducing at 350 ℃ for 4h. The reaction tail gas is kept warm and is analyzed by adopting an online chromatograph.
In a syngas conversion reaction 50At h, the CO conversion, CO, of examples 1 to 9 are recorded 2 Selectivity, product distribution and O/P (2-4), wherein: O/P (2-4) represents the ratio of olefin to alkane in the C2-C4 hydrocarbon compound. The following data were obtained:
as can be seen from the above table, in examples 1 to 4, the CO conversion rate was the highest in example 2, and accordingly, CO was the highest 2 The selectivity also peaks, mainly due to the gradual change of the configuration of the nitrogen-doped carbon material when the activation temperature is gradually increased from 600 ℃ to 800 ℃, and when the activation firing temperature is 700 ℃, the generated KOH-activated nitrogen-doped carbon material has the optimal configuration and can expose the most electron-rich sites, thereby contributing to the improvement of the catalytic activity.
Compared with the comparative examples 2, 5 and 6, when K element remains in the KOH activated nitrogen-doped carbon material, the activity of the catalyst is remarkably improved, and mainly because the K element can further promote the adsorption and dissociation of CO, the catalytic performance is improved.
Meanwhile, the catalytic activity of example 6 is lower than that of example 5, mainly because carbon deposition is generated when the content of the K element is too high, and the activity of the catalyst is influenced. Accordingly, in comparative examples 4 and 7, when K remains in the nitrogen-doped carbon material activated by KOH, the activity of the catalyst is also improved.
In addition, when K element remains in the nitrogen-doped carbon material activated by KOH, the ratio of alkene to alkane in the product can be effectively improved, and the improvement of the selectivity of alkene in the product is facilitated.
Using example 5 as the best example, the catalytic performance was compared to the catalysts of comparative examples 1 to 4, and at 15h of syngas conversion reaction, the CO conversion, CO of example 5 and comparative examples 1 to 4 were recorded 2 Selectivity, product distribution and O/P (2-4), wherein: O/P (2-4) representsThe ratio of alkene to alkane in the C2-C4 hydrocarbon compound. The following data were obtained:
as can be seen from the above table, the catalyst of example 5 has greatly improved catalytic activity compared to the conventional catalysts of comparative examples 1, 3 and 4. Specifically, in 15h of synthesis gas conversion reaction, KOH is adopted to activate the catalyst with the nitrogen-doped carbon material as the carrier, compared with activated carbon and SiO 2 And gamma-Al 2 O 3 The CO conversion rate of the catalyst used as the carrier is respectively improved by 9.96 times, 5.30 times and 3.49 times.
Meanwhile, the O/P (2-4) value of the catalyst in the example 5 is respectively improved by 0.40, 1.63 and 1.33 times compared with the O/P values of the catalysts in the comparative examples 1, 3 and 4, and the catalyst in the example 5 effectively improves the proportion of the low-carbon olefin in the product.
The catalyst of example 5 has a greatly improved catalytic activity relative to the catalyst of comparative example 2 which has not been activated with KOH. Specifically, when the synthesis gas is subjected to a conversion reaction for 15 hours, the catalyst using the KOH to activate the nitrogen-doped carbon material as the carrier has a CO conversion rate increased by 84% compared with the catalyst using the nitrogen-doped carbon material as the carrier, so that the KOH activation can effectively activate the nitrogen-doped carbon material, increase the specific surface area and the nitrogen doping degree of the nitrogen-doped carbon material, and change the percentage of different types of nitrogen, thereby changing the carbon-nitrogen configuration, promoting the generation of pyrrole nitrogen, exposing more electron-rich sites, and improving the catalytic activity.
The CO conversion during the syngas conversion reaction was recorded every 1h for the catalysts of example 5 and comparative example 2, plotted to give fig. 2.
As shown in the figure, the CO conversion rate of the catalyst in example 5 is always far greater than that of the catalyst in comparative example 2, the reactivity of the nitrogen-carbon material-supported Fe-based catalyst activated by koh has obvious performance advantages, and the catalyst has more electron-rich sites, improves the electron cloud density of Fe, promotes CO dissociation and the generation of active components, and thus significantly improves the reactivity.
The previous description of the disclosure is provided to enable any person skilled in the art to make or use the disclosure. Various modifications to the disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other variations without departing from the scope of the disclosure. Thus, the disclosure is not intended to be limited to the examples and designs described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (12)
1. A KOH-activated nitrogen-doped carbon material supported catalyst comprising a support comprising a KOH-activated nitrogen-doped carbon material and a metal active component.
2. The KOH activated nitrogen doped carbon material supported catalyst of claim 1, wherein the metal active component is one or a combination of more of Fe, co and Ni.
3. The KOH-activated nitrogen-doped carbon material-supported catalyst of claim 1, wherein the weight ratio of the support to the metal active component is (80-95): (5-20).
4. The KOH-activated nitrogen-doped carbon material supported catalyst of claim 1, wherein the KOH-activated nitrogen-doped carbon material has a residual K element content of 0 to 1.8%;
preferably, the content of K element remaining in the KOH-activated nitrogen-doped carbon material is 0.6%.
5. The KOH activated nitrogen-doped carbon material supported catalyst of claim 1, wherein the nitrogen-doped carbon material is an organo-metallic framework ZIF-8 derived nitrogen-doped carbon material.
6. A preparation method of a KOH activated nitrogen-doped carbon material supported catalyst is characterized by comprising the following steps:
preparing a nitrogen-doped carbon material;
uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating and drying, activating and roasting in an inert gas atmosphere, and washing to obtain a KOH-activated nitrogen-doped carbon material;
and (3) dipping the metal active component solution into the nitrogen-doped carbon material activated by the KOH, uniformly dispersing, drying and roasting to obtain the catalyst.
7. The method of claim 6, wherein the step of preparing the nitrogen-doped carbon material specifically comprises:
dissolving metal zinc salt and nitrogen-containing organic ligand in deionized water, and stirring to obtain white solid precipitate;
and washing and drying the white solid precipitate, and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material.
8. The preparation method of claim 7, wherein the metal zinc salt is zinc nitrate hexahydrate, the nitrogen-containing organic ligand is 2-methylimidazole, the weight ratio of the metal zinc salt to the nitrogen-containing organic ligand to deionized water is 0.11 (0.33-0.40) (60-70), and the roasting temperature in the step of washing and drying the white solid precipitate and roasting in an inert gas atmosphere to obtain the nitrogen-doped carbon material is 900-1100 ℃.
9. The method according to claim 6, wherein in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating and drying the resultant solution, activating and baking the resultant product in an inert gas atmosphere, and washing the resultant product to obtain a KOH-activated nitrogen-doped carbon material,
the mass ratio of KOH in the KOH solution to the nitrogen-doped carbon material is (1-3) to 1, the temperature of the activation roasting is 600-800 ℃, and the time of the activation roasting is 1-3 h.
10. The method according to claim 6, wherein in the step of uniformly dispersing the nitrogen-doped carbon material in a KOH solution, evaporating and drying the resultant solution, activating and baking the resultant product in an inert gas atmosphere, and washing the resultant product to obtain a KOH-activated nitrogen-doped carbon material,
the washing is specifically that firstly dilute hydrochloric acid is adopted for washing, and then deionized water is used for washing until the pH value is =7, so as to completely remove KOH; or directly washing with deionized water to ensure that the content of the residual K element is 0.6 to 1.8 percent;
preferably, the washing is directly washing with deionized water, so that the content of the residual K element is 0.6%.
11. The preparation method according to claim 6, wherein in the step of impregnating the KOH-activated nitrogen-doped carbon material with a metal active component solution, uniformly dispersing, drying and roasting,
the metal active component solution comprises one or more of Fe, co and Ni ion solutions, the drying temperature is 50-80 ℃, the drying time is 8-24 hours, the roasting temperature is 400-600 ℃, and the roasting time is 2-4 hours.
12. Use of a KOH activated nitrogen doped carbon material supported catalyst as claimed in any one of claims 1 to 5 or a KOH activated nitrogen doped carbon material supported catalyst prepared by a method as claimed in any one of claims 6 to 11 in a fischer-tropsch synthesis reaction to increase the conversion of synthesis gas and to increase the proportion of low carbon olefins in the product.
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