CN112973761A - Graphite phase carbon nitride composite material and preparation method and application thereof - Google Patents

Graphite phase carbon nitride composite material and preparation method and application thereof Download PDF

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CN112973761A
CN112973761A CN202110290163.8A CN202110290163A CN112973761A CN 112973761 A CN112973761 A CN 112973761A CN 202110290163 A CN202110290163 A CN 202110290163A CN 112973761 A CN112973761 A CN 112973761A
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powder
carbon nitride
composite material
stirring
nitride composite
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CN112973761B (en
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张建利
张玉玺
赵天生
马利海
高新华
马清祥
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Ningxia University
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    • 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
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a preparation method and application of a graphite phase carbon nitride composite material. The composite material is of a sheet structure, a basic unit is formed by heptazine rings, and a large number of hydroxyl and amino groups are arranged on the periphery of the structure after surface treatment, and can generate strong interaction with metal to facilitate the fixation of Fe active components. The catalyst has a unique electronic structure and good chemical stability, iron oxide is a main active phase of CO hydrogenation reaction, and the surface modified carbon nitride supported Fe catalyst provides a reliable scheme for preparing olefin by hydrogenation reaction.

Description

Graphite phase carbon nitride composite material and preparation method and application thereof
Technical Field
The invention relates to a layered composite material and a preparation method and application thereof, in particular to preparation of a graphite-phase carbon nitride-supported metal material and CO or CO thereof2Application of hydrogenation to olefin.
Background
Under the situation of shortage of petroleum energy in the world, the method has great strategic significance for vigorously developing the olefin preparation by taking the synthesis gas as the raw material. CO or CO2The low-carbon olefin is prepared by hydrogenation, and the method has the advantages of short flow and low energy consumption. However, the F-T product is limited by Anderson-Schulz-Flory (A-S-F) distribution, and the problems of wide product distribution range and low total olefin yield exist. Therefore, the research and development of the catalyst for the directional conversion of the target product have important research significance.
The graphite phase carbon nitride has larger specific surface area, the raw material price is low, and the preparation method is simple and convenient. The basic structure is formed by heptazine ring, so the compound has unique electronic structure effect and is widely used in photocatalysis reaction, and the application in the field of directly preparing olefin by hydrogenation is rarely reported. It is proved by research that hydroxyl groups on the surface of the catalyst can change the reaction path to reduce the selectivity of methane. The amino group is used as an electron-donating group, so that the surface electron density of the catalyst can be adjusted, and the olefin selectivity is improved. How to skillfully combine the two functional groups and apply the two functional groups to materials for directly preparing olefin is a very creative challenge.
The Fe catalyst has the advantages of low price, high water-gas shift activity and clean product (no sulfur and nitrogen) when being used for preparing olefin. The addition of the element auxiliary agent (Na, K, N, Mn) can change the surface electronic structure of the compound, obviously improve the olefin selectivity, but make the structure unstable and easy to inactivate. The metal dispersity can be improved by loading the catalyst on a carrier, so that the reaction activity and stability are improved, but the selectivity of olefin is reduced. The surface hydrophilic modification of the Fe catalyst can promote the diffusion of olefin, thereby reducing the secondary reaction of primary products and improving the selectivity of the olefin. Therefore, designing and preparing the carrier with the surface modified by hydrophilicity to load Fe is helpful to improve the selectivity of olefin and the stability of reaction. Experiments at home and abroad improve the reaction activity of photocatalytic degradation of organic pollutants by grafting amino and hydroxyl on the surface of carbon nitride through surface treatment. After characterization, the hydrophilicity of the carbon nitride surface is enhanced, and the electronic structure of the surface is changed. The Fe is loaded on the surface of carbon nitride to form an active phase iron nitride compound for Fischer-Tropsch synthesis, and although the iron nitride compound has higher olefin selectivity, the iron nitride compound has strong interaction with a carrier, so that the methane selectivity is higher. Therefore, the chemical treatment of the surface of the carbon nitride weakens the strong interaction between the carrier and the metal, thereby reducing the methane selectivity and having important research value.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a graphite phase carbon nitride composite material and a reaction application of the graphite phase carbon nitride composite material in olefin preparation through hydrogenation.
In the research of the invention, the seesaw effect of the material when the material is applied to the hydrogenation reaction for preparing olefin is also the technical problem to be solved by the invention. In research, it is found that carbon nitride directly loaded with metal such as Fe without surface treatment shows higher selectivity of low carbon olefin after being applied to carbon oxide hydrogenation reaction, but methane selectivity is high (more than 45%). The hydrogen peroxide treated carbon nitride has increased surface hydroxyl groups, and shows low methane selectivity (below 25%) in hydrogenation reaction, but the olefin selectivity is reduced (about 30%). After ammonia water surface treatment, the olefin selectivity is increased (more than 50 percent), and the low methane selectivity (less than 25 percent) is kept. The olefin prepared by the method mainly refers to low-carbon olefin, namely, ethylene, propylene and butylene.
In order to achieve the purpose, the invention adopts the following technical scheme:
the graphite phase carbon nitride composite material is of a sheet structure and is formed by heptazine rings, and after modification treatment, the surface of the material is surrounded with hydroxyl and amino functional groups to form functional group-carbon nitride; the material is loaded with nano metal particles, and the nano metal particles are polymerized on the surface of the functional group-carbon nitride and are in an amorphous state to coat a sheet shape; the metal particles account for 1-20% of the mass content of the carbon nitride.
The preparation method of the material comprises the following steps:
(1) calcining melamine, cooling to room temperature, and grinding to obtain powder A; (2) taking the powder A, stirring the powder A in a hydrogen peroxide solution, and performing suction filtration and drying after stirring to obtain powder B; (3) taking the powder B, stirring in ammonia water, putting into a reaction kettle after stirring, heating, taking out after setting time, carrying out suction filtration and drying to obtain powder C; (4) preparing a metal salt solution, and weighing powder B according to the mass parts: powder C = 0-1: 0.5 to 5, mechanically mixing to obtain powder D, adding a metal salt solution into the powder D, stirring, drying, roasting and grinding to obtain the target material.
The metal in the composite material is at least one of Fe, Co, Ni and Ru, and the metals La, Mn, K, Ce and Na are selectively added. The main metal is preferably Fe, and the auxiliary agent is preferably Mn, La, Na and K modification. The preparation method of the material disclosed by the invention has the advantages that the roasting temperature in the step (1) is 300-600 ℃, the heating rate is 2-10 ℃/min, and the time is 2-6 h. The concentration of hydrogen peroxide in the step (2) is 1-5 mol/L; in the step (3), the mass fraction of the ammonia water is 1-20%, the stirring time is 2-4 h, the heating temperature is 120-180 ℃, and the reaction time is 2-4 h.
The material is applied to CO or CO by combining multiple groups of experimental data to demonstrate2Preparing olefin by hydrogenation reaction, wherein a fixed bed reactor is adopted, and the operation conditions are as follows: 280-380 ℃ and 1-3 MPa for 1000-3000 h–1High contents of alpha-olefins can be obtained. With the aim of high olefin selectivity and low methane selectivity, it was found that there is a significant value in the addition ratio of powder B to powder C. The invention proposes: in the preparation step (4), powder B: when the proportion of the powder C is less than or equal to 1, the material is applied to CO hydrogenation under the atmosphere condition of H2the/CO = 1-3; powder B: when the ratio of the powder C is more than 1 and less than 2, the material is applied to CO and CO2Hydrogenation in mixed atmosphere under the condition of CO/CO2=0.5-50，H2/（CO+ CO2) 1-3; powder B: when the ratio of the powder C is more than 2 and less than 5, the material is applied to CO2Hydrogenation under the atmosphere condition of H2/CO2 = 1-3, shows very good olefin yield, and has industrial application prospect。
The beneficial technical effects obtained by the invention are as follows:
(1) the catalyst prepared by the invention can catalyze CO or CO simultaneously2Producing olefins suitable for coal-based, biomass-based and natural gas-based synthesis gas, and containing CO2The reaction process for preparing olefin by coproducing raw materials has a wide application scene.
(2) The method adopts the carbon nitride with the sheet structure, can well promote the product diffusion and shorten the reaction distance. Meanwhile, the graphite-phase carbon nitride has alkaline surface, contains an electronic assistant N, has high heat-resistant temperature, has a flaky structure with larger specific surface area and stable chemical property, and can obviously improve the stability and catalytic activity of the catalyst.
(3) According to the invention, from the aspect of atomic layer deposition, metal particles are uniformly dispersed on the carbon nitride composite material, so that the acid sites on the surface of the composite material can be effectively weakened, and the side reactions of product isomerization or hydrogenation are reduced.
(4) The material has strong functions between functional groups and metals, can prevent metal migration loss, weaken carbon deposition to inactivate, prolong the service life of the catalyst, simultaneously avoid low-carbon olefin from being hydrogenated to form alkane, and ensure that the product has high selectivity of gas-phase low-carbon olefin through the synergistic effect of the alkaline sites on the surface of the catalyst after surface modification and active hydroxyl groups, thereby being expected to be applied in industry.
(5) The preparation method is simple, the precursor material of the graphite-phase carbon nitride is rich and cheap in source, and the surface treatment method is simple, non-toxic, environment-friendly and free of heavy metal pollution, so that the method is suitable for industrial large-scale production.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In the following examples, all the starting components, unless otherwise specified, are commercially available products well known to those skilled in the art.
Example 1
Adding 10g of melamine into a crucible, placing the crucible into a muffle furnace, roasting for 4h at the temperature of 550 ℃ and the heating rate of 2.5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 6 g of the powder A into a beaker, adding 200 mL of 1 mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 250 mL of ammonia water with the mass fraction of 2.5 wt%, magnetically stirring for 2h, putting into an oven, reacting at 150 ℃ for 3h, taking out, filtering, and drying to obtain powder C; taking 1g of each of the powder B and the powder C, and mechanically mixing to obtain powder D. Preparing 2mol/L ferric nitrate solution. 2mL of an iron nitrate solution was added to each of powder B, powder C and powder D, each of which had an equivalent mass of 2 g. The mixture was ultrasonically stirred and dried overnight. And respectively placing the mixture in a muffle furnace, heating the mixture to 300 ℃ in the air atmosphere, calcining the mixture for 3 hours at constant temperature, and obtaining iron-containing powder B, iron-containing powder C and an iron-containing carbon nitride composite material after the calcination is finished. The three materials are respectively appliedThe method is used for CO hydrogenation reaction. The reaction condition is H2/CO =2, temperature 300 ℃, pressure 1.5 MPa, space velocity (GHSV) 1000 h-1The results of the catalytic performance test are shown in Table 1.
Example 2
Adding 10g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 600 ℃ and the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 2mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 100 mL of ammonia water with the mass fraction of 3 wt%, magnetically stirring for 2h, putting into a drying oven, reacting at 180 ℃ for 3h, taking out, filtering, and drying to obtain powder C; and (3) taking 0.5g of the powder B and 2g of the powder C, mechanically mixing to obtain a powder D, adding 3mL of a 5mol/L ferric nitrate solution, ultrasonically stirring, and drying overnight. And placing the obtained powder in a muffle furnace, heating to 400 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. The method is applied to CO hydrogenation reaction. The reaction condition is H2/CO =2, temperature 300 ℃, pressure 2.0 MPa, space velocity (GHSV) 2000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 3
Adding 10g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 600 ℃ and the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 2mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 10wt%, magnetically stirring for 2h, putting into a drying oven, reacting at 180 ℃ for 3h, taking out, filtering, and drying to obtain powder C; and (3) taking 1g of the powder B and 2g of the powder C, mechanically mixing to obtain powder D, adding 3mL of 5mol/L nickel nitrate solution, ultrasonically stirring, and drying overnight. And placing the obtained powder in a muffle furnace, heating to 400 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the nickel-containing carbon nitride composite material after calcining. The method is applied to CO hydrogenation reaction. The reaction condition is H2/CO =3, temperature 320 ℃, pressure 2.0 MPa, emptyThe speed (GHSV) is 1000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 4
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 6 hours at the temperature of 300 ℃ and the heating rate of 2 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 100 mL of 5mol/L hydrogen peroxide, stirring for 3 hours, and performing suction filtration and drying to obtain powder B. Putting 5g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 20 wt%, magnetically stirring for 2h, putting into an oven, reacting at 200 ℃ for 5h, taking out, filtering, and drying to obtain powder C; powder B1 g and powder C2 g were mechanically mixed to obtain powder D, and powder D was added to 10mL of a solution prepared from iron nitrate 4.4g, lanthanum nitrate 1.2g and manganese nitrate 0.25g, and the mixture was ultrasonically stirred and dried overnight. And placing the obtained powder in a muffle furnace, heating to 500 ℃ in the air atmosphere, calcining for 3h at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. The method is applied to CO hydrogenation reaction. The reaction condition is H2/CO =2, temperature 300 ℃, pressure 2.0 MPa, space velocity (GHSV) 2000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 5
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 600 ℃ and the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 5mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 3 wt%, magnetically stirring for 2h, putting into a drying oven, reacting at 180 ℃ for 3h, taking out, filtering, and drying to obtain powder C; and (3) taking 2g of the powder B and 1g of the powder C, mechanically mixing to obtain powder D, adding 5mL of a 10mol/L ferric nitrate solution, ultrasonically stirring, and drying overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Applied to the volume fraction of 60 percent H2，30%CO，10%CO2Reacting in atmosphere. The temperature is 300 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 2000 h-1Promoting the production ofThe results of the chemical property tests are shown in Table 2.
Example 6
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 600 ℃ and the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 5mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 3 wt%, magnetically stirring for 2h, putting into a drying oven, reacting at 180 ℃ for 3h, taking out, filtering, and drying to obtain powder C; powder B3 g and powder C2 g were mechanically mixed to obtain powder D, and powder D was added to 10mL of a solution prepared from cobalt nitrate 1.2g, iron nitrate 0.5g, potassium nitrate 0.15g, and manganese nitrate 0.25g, followed by ultrasonic stirring and drying overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Applied to the volume fraction of 60 percent H2，30%CO，10%CO2Reacting in atmosphere. The temperature is 300 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 2000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 7
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 400 ℃ and at the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 5mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 10wt%, magnetically stirring for 2h, putting into an oven, reacting at 220 ℃ for 5h, taking out, filtering, and drying to obtain powder C; and (3) taking 1g of the powder B and 3g of the powder C, mechanically mixing to obtain powder D, adding 5mL of a 10mol/L ferric nitrate solution, ultrasonically stirring, and drying overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Application to H2/CO2Reaction under an atmosphere of = 3. The temperature is 300 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 1000 h-1The results of the catalytic performance test are shown inTable 2.
Example 8
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 4 hours at the temperature of 600 ℃ and the heating rate of 5 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 5g of the powder A into a beaker, adding 50 mL of 5mol/L hydrogen peroxide, magnetically stirring for 2 hours, and then carrying out suction filtration and drying to obtain powder B. Putting 3g of the powder B into a reaction kettle, adding 50 mL of ammonia water with the mass fraction of 3 wt%, magnetically stirring for 2h, putting into a drying oven, reacting at 180 ℃ for 3h, taking out, filtering, and drying to obtain powder C; powder B1 g and powder C3 g were mechanically mixed to obtain powder D, and powder D was added to 10mL of a solution prepared from cobalt nitrate 1.2g, iron nitrate 0.5g, potassium nitrate 0.15g, and manganese nitrate 0.25g, followed by ultrasonic stirring and drying overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Application to H2/CO2Reaction under an atmosphere of = 3. The temperature is 300 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 2000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 9
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 3h at the temperature of 500 ℃ and the heating rate of 10 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 10g of the powder A into a beaker, adding 100 mL of 3mol/L hydrogen peroxide, magnetically stirring for 2 hours, and performing suction filtration and drying to obtain powder B. Putting 5g of the powder B into a reaction kettle, adding 100 mL of ammonia water with the mass fraction of 15 wt%, magnetically stirring for 6h, putting into a drying oven, reacting at 200 ℃ for 4h, taking out, filtering, and drying to obtain powder C; and (3) taking 1g of the powder B and 4g of the powder C, mechanically mixing to obtain powder D, adding the powder D into 10mL of a solution prepared from 4.4g of ferric nitrate, 0.5g of nickel nitrate, 0.25g of sodium nitrate, 0.5g of lanthanum nitrate and 0.1g of cerium nitrate, ultrasonically stirring, and drying overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Application to H2/CO2Reaction under an atmosphere of = 2. The temperature is 320 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 3000 h-1The results of the catalytic performance tests are shown in Table 2.
Example 10
Adding 20g of melamine into a crucible with a cover, placing the crucible into a muffle furnace, roasting for 3h at the temperature of 500 ℃ and the heating rate of 10 ℃/min, cooling to room temperature, and fully grinding to obtain powder A. And (3) putting 10g of the powder A into a beaker, adding 100 mL of 3mol/L hydrogen peroxide, magnetically stirring for 2 hours, and performing suction filtration and drying to obtain powder B. Putting 5g of the powder B into a reaction kettle, adding 100 mL of ammonia water with the mass fraction of 15 wt%, magnetically stirring for 6h, putting into a drying oven, reacting at 200 ℃ for 4h, taking out, filtering, and drying to obtain powder C; powder B1 g and powder C4 g were mechanically mixed to obtain powder D, and powder D was added to a 10mL solution prepared from 4.4g of ferric nitrate, 1.5g of manganese nitrate, 0.25g of potassium nitrate, 0.2g of lanthanum nitrate, and 0.1g of cerium nitrate, and the mixture was ultrasonically stirred and dried overnight. And placing the obtained powder in a muffle furnace, heating to 600 ℃ in the air atmosphere, calcining for 5 hours at constant temperature, and obtaining the iron-containing carbon nitride composite material after calcining. Application to H2/CO2Reaction under an atmosphere of = 2. The temperature is 320 ℃, the pressure is 2.0 MPa, and the space velocity (GHSV) is 3000 h-1The results of the catalytic performance tests are shown in Table 2.
All the carbon nitride carriers are sheet materials, and the sheet structures of the carbon nitride carriers are not damaged after surface modification. The bulk material on the surface is loaded with active component iron.
As can be seen from table 1, the carbon nitride without surface treatment directly supports Fe and shows higher selectivity of low-carbon olefin after being applied to the CO hydrogenation reaction, but the methane selectivity is high. The hydroxyl on the surface of the carbon nitride is increased after the hydrogen peroxide treatment, and the carbon nitride is used for CO hydrogenation reaction after loading Fe, so that the methane selectivity is reduced, but the olefin selectivity is reduced. After ammonia water surface treatment, the selectivity of olefin is increased.
As can be seen from Table 2, the catalyst of the present invention is applied to CO or CO2Or a mixed atmosphere, the catalyst shows higher olefin selectivity and lower methane selectivity.
Table 1 results of sample property testing of example 1
Catalyst and process for preparing same CO conversion (%) CO2Selectivity (%) CH4(%) C2-C4 =(%) C2-C4 0(%) C5 +(%) O/P
Iron-containing powder B 38.78 28.61 21.5 35.72 9.89 32.89 3.61
Iron-containing powder C 35.68 17.91 46.06 38.52 11.11 4.31 4.23
Iron-containing carbon nitride composite material 40.21 16.34 25.4 46.16 11.21 17.23 3.78
TABLE 2 results of sample Performance testing of examples 2-10
Catalyst and process for preparing same CO/CO2 conversion (%) CO2/CO Selectivity (%) CH4(%) C2-C4 =(%) C2-C4 0(%) C5 +(%) O/P
Example 2 42.21 16.34 25.67 45.94 11.15 17.24 4.12
Example 3 40.48 14.35 26.72 46.39 9.54 17.35 4.86
Example 4 37.97 12.17 28.52 47.81 7.73 15.94 6.18
Example 5 30.11 12.86 14.87 46.19 12.3 26.64 3.75
Example 6 32.26 13.42 16.41 48.49 12.1 23 4
Example 7 24.72 28.59 5.51 68.61 20.84 5.04 3.29
Example 8 31.46 32.43 6.24 65.13 17.56 11.07 3.71
Example 9 38.91 36.77 4.55 71.91 15.91 7.63 4.52
Example 10 40.16 38.96 3.49 75.16 15.46 5.89 4.86

Claims (6)

1. A graphite phase carbon nitride composite material is characterized in that the carbon nitride composite material is of a sheet structure and is composed of heptazine rings, and hydroxyl and amino functional groups are surrounded on the surface of the material to form functional group-carbon nitride; the material is loaded with nano metal particles, and the nano metal particles are polymerized on the surface of the functional group-carbon nitride and are in an amorphous state to coat a sheet shape; the metal particles account for 1-20% of the mass content of the carbon nitride; the preparation method of the material comprises the following steps:
(1) calcining melamine, cooling to room temperature, and grinding to obtain powder A;
(2) taking the powder A, stirring the powder A in a hydrogen peroxide solution, and performing suction filtration and drying after stirring to obtain powder B;
(3) taking the powder B, stirring in ammonia water, putting into a reaction kettle after stirring, heating, taking out after setting time, carrying out suction filtration and drying to obtain powder C;
(4) preparing a metal salt solution, and weighing powder B according to the mass parts: powder C = 0-1: 0.5 to 5, mechanically mixing to obtain powder D, adding a metal salt solution into the powder D, stirring, drying, roasting and grinding to obtain the target material.
2. The graphite phase carbon nitride composite material according to claim 1, wherein the metal is at least one of Fe, Co, Ni and Ru, and the metals La, Mn, K, Ce and Na are selectively added.
3. The graphite phase carbon nitride composite material of claim 1, wherein: in the preparation step (4), powder B: when the proportion of the powder C is less than or equal to 1, the material is applied to CO hydrogenation under the atmosphere condition of H2the/CO = 1-3; powder B: when the ratio of powder C is more than 1 and less than 2, the material is applied to CO and CO2Hydrogenation in mixed atmosphere under the condition of CO/CO2=0.5-50，H2/（CO+ CO2) 1-3; powder B: when the ratio of powder C is more than 2 and less than 5, the material is applied to CO2Hydrogenation under the atmosphere condition of H2/CO2 =1~3。
4. The graphite phase carbon nitride composite material according to claim 1, wherein the calcination temperature in the step (1) of the preparation method is 300-600 ℃, the temperature rise rate is 2-10 ℃/min, and the time is 2-6 h.
5. The graphite phase carbon nitride composite material according to claim 1, wherein the concentration of hydrogen peroxide in the step (2) of the preparation method is 1-5 mol/L; in the step (3), the mass fraction of the ammonia water is 1-20%, the stirring time is 2-4 h, the heating temperature is 120-180 ℃, and the reaction time is 2-4 h.
6. The application of the graphite phase carbon nitride composite material is characterized in that: application of composite material to CO or CO2The hydrogenation reaction for preparing ethylene, propylene and butylene adopts a fixed bed reactor, and the operation conditions are as follows: 280-380 ℃ and 1-3 MPa for 1000-3000 h–1。
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