CN118183792A - Method for synthesizing ammonia by using Co-supported porous carbon catalyst based on heavy biological oil - Google Patents
Method for synthesizing ammonia by using Co-supported porous carbon catalyst based on heavy biological oil Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 52
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 52
- 239000012075 bio-oil Substances 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 9
- 238000009656 pre-carbonization Methods 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000000197 pyrolysis Methods 0.000 abstract description 8
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- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
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- 238000010494 dissociation reaction Methods 0.000 abstract description 2
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- 238000010438 heat treatment Methods 0.000 description 11
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WPWCLBXYKATSMD-UHFFFAOYSA-N [2-(tert-butylcarbamoylamino)-2-oxoethyl] 3-cyclopentylpropanoate Chemical compound CC(C)(C)NC(=O)NC(=O)COC(=O)CCC1CCCC1 WPWCLBXYKATSMD-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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Abstract
The invention relates to the technical field of distributed mild ammonia synthesis, in particular to a method for synthesizing ammonia by using a Co-supported porous carbon catalyst based on heavy biological oil. The method utilizes industrial waste, namely heavy biological oil, and synthesizes a cascade porous carbon-based Co catalyst (Co-PBs) through a Co-catalytic pyrolysis method. Cobalt on the one hand acts as a pyrolysis catalyst to promote pyrolysis of heavy bio-oil, forming a porous biochar framework with a larger surface area. On the other hand, the co-catalytic pyrolysis leads to more uniform loading of cobalt, and as a plasma-assisted ammonia synthesis catalyst, the adsorption of free radicals and the dissociation of NH 3 are further promoted, and the performance of ammonia synthesis is enhanced. Co-PBs exhibit plasma-assisted ammonia synthesis rates as high as 1.605 mmol/g.h due to enhanced mass transfer rates and more uniform transition metal active site distribution. Meanwhile, the extremely high stability of Co-PBs enables the Co-PBs to keep stable performance in 24 cycles and 40 hours of long-time reaction, and the Co-PBs have great application potential.
Description
Technical Field
The invention relates to the technical field of distributed mild ammonia synthesis, in particular to a method for synthesizing ammonia by using a Co-supported porous carbon catalyst based on heavy bio-oil.
Background
Ammonia is an extremely important chemical raw material and is one of the inorganic materials with highest yield in the world. Meanwhile, ammonia has the unique advantages of high hydrogen storage density (17.7 wt%), cleanliness, high efficiency, reproducibility and the like, and is a novel zero-carbon fuel and hydrogen storage material with great potential. Whereas the traditional ammonia synthesis process, the haber-bosch process, needs to be carried out at high temperatures up to 500 ℃ and high pressures of 150-300 bar. The centralized haber process consumes 2% of the energy worldwide each year with emissions exceeding 4.2 hundred million tons of CO 2. Thus, in recent years, more and more emerging green low-carbon ammonia synthesis technologies, such as photocatalytic ammonia synthesis, electrochemical ammonia synthesis, chemical-looping ammonia synthesis, biological nitrogen fixation, have been developed. The plasma assisted ammonia synthesis technology can be coupled with distributed renewable energy sources, synthesizes ammonia through a zero carbon process at normal temperature and normal pressure, has a rate exceeding that of the Haber method ammonia synthesis in theory, and is considered as a green ammonia synthesis technology with great application potential. The plasma-assisted synthesis of ammonia can be completed only by a small plasma generator, can be well coupled with renewable energy sources such as solar energy, wind energy and the like, and can avoid energy consumption in the industrial product transportation process by in-situ reaction in remote areas. The catalysts which are widely studied and used at present comprise Al 2O3,SiO2, mesoporous molecular sieves and organic metal frameworks, and the common characteristics of the catalysts are that the catalysts have rich porous structures and huge specific surface areas, so that the mass transfer performance of free radicals can be enhanced and the number of active sites can be increased. They have the disadvantage that it is difficult to tailor the pore structure to enhance the plasma-assisted ammonia synthesis performance. At the same time, these materials are expensive and the structure is susceptible to collapse and deactivation under high electric field conditions for extended periods of time. The heavy biological oil, which is waste in the biomass pyrolysis process, can be used as an ashless source to synthesize carbon materials on one hand, has the advantage of removing the original biomass framework structure, and the framework structure is easy to regulate and control. On the other hand, the main solutions using heavy bio-oils are currently faced with a number of difficulties, and therefore the conversion of bio-oils into valuable carbon materials is a potential way of using such waste. The Co-supported porous carbon catalyst prepared based on heavy biological oil is prepared from the byproduct heavy biological oil in the biomass pyrolysis production of biodiesel serving as a raw material for plasma-assisted ammonia synthesis, so that the cost and the environmental hazard in the catalytic pyrolysis treatment process are avoided, and an effective strategy is provided for a future green ammonia synthesis process.
Disclosure of Invention
The invention aims to: the invention aims to provide a method for synthesizing ammonia by using a Co-supported porous carbon catalyst based on heavy biological oil.
The technical scheme is as follows: according to the method for synthesizing ammonia by using the Co-supported porous carbon catalyst based on heavy bio-oil, ammonia is synthesized by plasma assistance, the Co-supported porous carbon catalyst is added into a plasma assistance ammonia synthesis reactor, N 2 and H 2 are conveyed into the plasma assistance ammonia synthesis reactor, and ammonia is synthesized by reaction; wherein the Co-supported porous carbon catalyst is prepared by the steps of: (1) mixing a Co source and heavy biological oil to obtain a material A; (2) Pre-carbonizing the material A, and grinding into powder to obtain powder B; (3) And mixing the powder B with alkali, carbonizing the uniformly grinded mixture, and grinding the obtained product into powder C, wherein the powder C is the Co-supported porous carbon catalyst.
Further, a Co-supported porous carbon catalyst is added into the plasma-assisted ammonia synthesis reactor, N 2 and H 2 are conveyed into the plasma-assisted ammonia synthesis reactor, and ammonia is synthesized by reaction.
Further, the temperature of ammonia synthesis is 200-400 ℃.
Further, N 2 and H 2 are fed into the plasma-assisted ammonia synthesis reactor at a flow rate of 1:7 to 7:1 ratio.
Further, in the step (1), co source is Co (the mass ratio of NO 3)2·6H2O,Co(NO3)2·6H2 O to heavy bio-oil is 1:10-20).
Further, in the step (2), the pre-carbonization condition is that the temperature is raised to 500-550 ℃ at a speed of 5-10 ℃/min under the inert gas atmosphere and kept for 1-1.5 h for pre-carbonization.
Further, in the step (3), the alkali is NaOH, and the addition amount of the NaOH is 1-3 times of the mass of the powder B.
Further, in the step (3), the carbonization condition is that the temperature is raised to 800-850 ℃ at a rate of 5-10 ℃/min under the inert gas atmosphere and maintained for 2-2.5 h.
Further, in the step (3), the powder C is washed with an acid solution and water for several times, salts and impurities in the powder C are removed, and the obtained product is dried to obtain the Co-supported porous carbon catalyst.
Further, in the step (4), the acid solution is HCl solution.
The invention synthesizes a cascade porous carbon-based Co catalyst (Co-PBs) by utilizing industrial waste, namely heavy biological oil, through a Co-catalytic pyrolysis method. Cobalt on the one hand acts as a pyrolysis catalyst to promote pyrolysis of heavy bio-oil, forming a porous biochar framework with a larger surface area. On the other hand, the co-catalytic pyrolysis leads to more uniform loading of cobalt, and as a plasma-assisted ammonia synthesis catalyst, the adsorption of free radicals and the dissociation of NH 3 are further promoted, and the performance of ammonia synthesis is enhanced. Co-PBs exhibit plasma-assisted ammonia synthesis rates as high as 1.605 mmol/g.h due to enhanced mass transfer rates and more uniform transition metal active site distribution. Meanwhile, the extremely high stability of Co-PBs enables the Co-PBs to keep stable performance in 24 cycles and 40 hours of long-time reaction, and the Co-PBs have great application potential.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the Co-supported porous carbon catalyst supported by Co is prepared by a Co-catalytic pyrolysis method and is applied to the field of plasma-assisted ammonia synthesis. The Co-supported porous carbon material prepared by the invention is of a loose porous hollow carbon skeleton structure, which is beneficial to enhancing the mass transfer performance of the material, so that more free radicals can be contacted with active sites, and the rate of synthesizing ammonia is increased;
the synthetic ammonia rate of the Co-supported porous carbon material used in the invention reaches 1.605 mmol/g.h, which exceeds the Co-supported porous biological carbon material prepared by a direct loading method and an impregnation method, and meanwhile, the preparation process of the catalyst is greatly simplified, and Co is used as a pyrolysis catalyst on one hand and as a plasma-assisted synthetic ammonia active metal on the other hand, so that the method is a strategy of 'one stone and two birds'.
The method for synthesizing the Co-supported porous carbon material by the plasma assisted ammonia has the advantages that the synthetic ammonia rate is hardly changed within 40h, and the stability is higher.
The plasma-assisted ammonia synthesis method of the Co-loaded porous carbon material is compared with the synthesis ammonia rate in 24 cycle periods, and the fact that the synthesis ammonia rate can be stabilized at a higher value after the 5 th cycle and cannot decay any more is found, so that the method has good circularity.
Drawings
FIG. 1 is a schematic diagram of a preparation process flow of the Co-supported porous carbon material.
FIG. 2 is a diagram showing the structure of the Co-supported porous carbon material of the present invention under a scanning electron microscope.
FIG. 3 is a schematic illustration of a reaction and testing apparatus for plasma-assisted ammonia synthesis according to the present invention.
FIG. 4 is a comparison of ammonia synthesis rates of Co-supported porous carbon materials according to the present invention and commercial materials.
FIG. 5 shows the ammonia synthesis rate of the Co-supported porous carbon material of the present invention at different gas ratios.
FIG. 6 shows the ammonia synthesis rates of the Co-supported porous carbon material of the present invention at different temperatures.
FIG. 7 shows the change of the synthesis ammonia rate of the Co-supported porous carbon material of the present invention during a long-term reaction for 40 hours.
FIG. 8 is a graph showing the variation of the ammonia synthesis rate of the Co-supported porous carbon material of the present invention over 24 cycles of reaction.
Detailed Description
As shown in fig. 1, the embodiment of the invention provides a preparation method of a Co-supported porous carbon catalyst based on heavy bio-oil, which comprises the following steps:
(1) Mixing a Co source and heavy biological oil to obtain a material A; preferably, the Co source is Co (the mass ratio of NO 3)2·6H2O,Co(NO3)2·6H2 O to heavy bio-oil is 1:10-20).
(2) Pre-carbonizing the material A, and grinding into powder to obtain powder B; wherein the pre-carbonization condition is that the temperature is raised to 500-550 ℃ at a speed of 5-10 ℃/min under the inert gas atmosphere and kept for 1-1.5 h for pre-carbonization.
(3) Mixing the powder B with alkali, performing secondary carbonization on the mixture after uniform grinding, heating to 800-850 ℃ at a speed of 5-10 ℃/min under the inert gas atmosphere, maintaining for 2-2.5h, grinding the obtained product into powder C, washing the powder C for a plurality of times by using an acid solution and water respectively, removing salt and impurities in the powder C, and drying the obtained product to obtain the Co-supported porous carbon catalyst (Co-PBs). Wherein,
Preferably, the base is NaOH, and the addition amount of NaOH is 1-3 times of the mass of the powder B.
The heavy bio-oil used in the examples of the present invention consisted of 10% acid, 55% phenol, 10% ketone, 5% aldehyde, 15% ester, 5% alcohol, wherein the contents of C and O were 58% and 36%, respectively.
Example 1
The embodiment provides a preparation method of a Co-supported porous carbon catalyst based on heavy biological oil, which comprises the following steps:
(1) Adding 0.5g Co (NO 3)2·6H2 O and 10g heavy biological oil) into a beaker, and fully stirring for 5min at room temperature to obtain a material A;
(2) Placing the material A in a quartz boat, heating to 500 ℃ at a speed of 5 ℃/min in a tubular furnace under Ar atmosphere, maintaining for 1h for pre-carbonization, naturally cooling to room temperature, and grinding into powder B;
(3) Mixing powder B with NaOH with 3 times of mass, grinding uniformly, placing in an alumina boat, heating to 800 ℃ at a speed of 10 ℃/min in an Ar atmosphere in a tube furnace, maintaining for 2 hours, naturally cooling to room temperature, and grinding into powder C;
(4) Washing the powder C with 2mol/L HCl solution and distilled water 6 times each to remove salts and impurities;
(5) And drying the obtained sample at 100 ℃ for 12 hours to obtain the Co-supported porous carbon catalyst supported by Co.
The preparation flow chart of the Co-supported porous carbon material is shown in figure 1, and three processes of pre-carbonization, secondary carbonization, neutralization and cleaning are carried out to successfully synthesize the porous biochar material with extremely high specific surface area and excellent pore structure.
The surface morphology is shown in fig. 2, and the material presents a loose and porous hollow carbon skeleton structure, which is beneficial to enhancing the mass transfer performance, so that more free radicals can contact with active sites, and the rate of synthesizing ammonia is increased.
Example 2
The embodiment provides a preparation method of a Co-supported porous carbon catalyst based on heavy biological oil, which comprises the following steps:
(1) Adding 0.5g Co (NO 3)2·6H2 O and 5.0g heavy biological oil) into a beaker, and fully stirring for 5min at room temperature to obtain a material A;
(2) Placing the material A in a quartz boat, heating to 500 ℃ at a speed of 5 ℃/min in a tubular furnace under Ar atmosphere, maintaining for 1h for pre-carbonization, naturally cooling to room temperature, and grinding into powder B;
(3) Mixing powder B with NaOH with 3 times of mass, grinding uniformly, placing in an alumina boat, heating to 800 ℃ at a speed of 10 ℃/min in an Ar atmosphere in a tube furnace, maintaining for 2 hours, naturally cooling to room temperature, and grinding into powder C;
(4) Washing the powder C with 2mol/L HCl solution and distilled water 6 times each to remove salts and impurities;
(5) And drying the obtained sample at 100 ℃ for 12 hours to obtain the Co-supported porous carbon catalyst supported by Co.
Example 3
The embodiment provides a preparation method of a material of a plasma-assisted ammonia synthesis method of a Co-supported porous carbon catalyst based on heavy biological oil,
The method comprises the following steps:
(1) Adding 0.5g Co (NO 3)2·6H2 O and 10g heavy biological oil) into a beaker, and fully stirring for 5min at room temperature to obtain a material A;
(2) Placing the material A in a quartz boat, heating to 550 ℃ at a speed of 10 ℃/min in a tubular furnace under Ar atmosphere, maintaining for 1.5h for pre-carbonization, naturally cooling to room temperature, and grinding into powder B;
(3) Mixing powder B with NaOH with the mass being 1 time, grinding uniformly, placing in an alumina boat, heating to 850 ℃ at a speed of 5 ℃/min in a tubular furnace under Ar atmosphere, keeping for 2.5 hours, naturally cooling to room temperature, and grinding into powder C;
(4) Washing the powder C with 2mol/L HCl solution and distilled water 6 times each to remove salts and impurities;
(5) And drying the obtained sample at 100 ℃ for 12 hours to obtain the Co-supported porous carbon catalyst supported by Co.
Example 4
The present example provides a plasma assisted ammonia synthesis process using a Co supported porous carbon catalyst prepared based on heavy bio-oil.
As shown in FIG. 3, the device for synthesizing ammonia by plasma assistance in the invention is characterized in that nitrogen and hydrogen are fully mixed before entering a reactor, the power of the plasma is controlled by a power generator and a voltage regulator, and the amount of the synthesized ammonia is measured by a dilute sulfuric acid solution and a conductivity meter, and the device comprises the following specific steps:
(1) Connecting a high voltage electrode in the plasma-assisted ammonia synthesis reactor to a high voltage power supply;
(2) Wrapping a stainless steel mesh outside the reactor as a low-voltage electrode and grounding;
(3) The fixed microporous substrate carrying the catalyst powder is arranged at the lowest part of the high-voltage electrode, and the Co-loaded porous carbon-based material prepared in the embodiment 1 is filled in the fixed microporous substrate;
(4) Heating the reactor to 200 ℃ through a tube furnace;
(5) N 2 and H 2 are delivered into a reactor in a ratio of 1:1, ammonia is synthesized by reaction, wherein the flow rates of N 2 and H 2 are both 50 ml/min;
(6) The amount of synthetic ammonia was determined by dilute sulfuric acid solution and conductivity meter.
Example 5
This example provides the use of the Co-supported porous carbon catalysts prepared in example 1 and example 2 in ammonia synthesis. Examine the effect of different catalysts on the synthesis of ammonia: ammonia was synthesized according to the procedure described in example 4, co/Al 2O3 being a commercially available 5% mass fraction porous alumina catalyst, with the ratio of N 2 to H 2 in step (5) set to 1:1, to synthesize ammonia.
As shown in FIG. 4, the synthesis ammonia rate of the Co-supported porous carbon material in the embodiment 1 used in the invention reaches 1.605 mmol/g.h, and the Co-supported porous carbon material exceeds 10% by mass, so that the catalyst preparation process is greatly simplified, and Co is a strategy of 'one stone and two birds' on the one hand as a pyrolysis catalyst and on the other hand as a plasma-assisted synthesis ammonia active metal.
The effect of the different ratios of H 2 and N 2 on the effect of synthetic ammonia was examined: ammonia was synthesized following the procedure described in example 3, and the flow rates of H 2 and N 2 were adjusted to achieve 1:7, 2:6, 3:5, 4:4, 5:3, 6:2, 7:1 ratios of H 2 and N 2, respectively, to produce final ammonia. The results are shown in FIG. 5, where the synthetic ammonia rate was measured as a function of the ratio of H 2 to N 2, at a ratio of 1: maximum value is reached at 1.
Examine the influence of different heating temperatures on the effect of synthetic ammonia: ammonia was synthesized according to the procedure described in example 3, and the heating temperature in step (4) was set to 50, 100, 200, 300, 400. As a result, as shown in FIG. 6, the plasma ammonia synthesis rate was measured as a function of temperature, and increased most rapidly with temperature before 200 ℃.
According to the measurement results, the rate of the plasma-assisted ammonia synthesis method of the Co-supported porous carbon material is far higher than that of the current common method, and the Co-supported porous carbon material has potential of industrial application.
Example 6
Stability and circularity of plasma-assisted ammonia synthesis method of Co-supported porous carbon catalyst prepared based on heavy biological oil
The method comprises the following steps:
(1) Connecting a high voltage electrode in the plasma-assisted ammonia synthesis reactor to a high voltage power supply;
(2) Wrapping a stainless steel mesh outside the reactor as a low-voltage electrode and grounding;
(3) The lowest part of the high-voltage electrode is provided with a fixed micropore substrate for bearing catalyst powder, and Co-loaded porous carbon-based materials are filled into the fixed micropore substrate;
(4) Heating the reactor to 200 ℃ through a tube furnace;
(5) N 2 and H 2 are delivered into a reactor at a flow rate of 50ml/min for reaction to synthesize ammonia;
(6) The amount of synthetic ammonia was determined by dilute sulfuric acid solution and conductivity meter.
The stability of the plasma-assisted ammonia synthesis method based on the Co-supported porous carbon material in 40h is shown in figure 7, and the ammonia synthesis rate of the Co-supported porous carbon material used as a catalyst hardly changes in 40h, thus proving the application value of the Co-supported porous carbon material as an industrial catalyst.
The synthesis ammonia rate of the Co-supported porous carbon catalyst prepared based on heavy biological oil in the plasma-assisted ammonia synthesis method in 24 cycle periods is shown in figure 8, and after the 5 th cycle, the synthesis ammonia rate can be stabilized at a higher value without attenuation, thus showing great potential in future industrialized application.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited thereto, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method for synthesizing ammonia by using a Co-supported porous carbon catalyst based on heavy bio-oil is characterized in that the method comprises the steps of adding the Co-supported porous carbon catalyst into a plasma-assisted ammonia synthesis reactor, conveying N 2 and H 2 into the plasma-assisted ammonia synthesis reactor, and reacting to synthesize ammonia; wherein the Co-supported porous carbon catalyst is prepared by the steps of: (1) mixing a Co source and heavy biological oil to obtain a material A; (2) Pre-carbonizing the material A, and grinding into powder to obtain powder B; (3) And mixing the powder B with alkali, carbonizing the uniformly grinded mixture, and grinding the obtained product into powder C, wherein the powder C is the Co-supported porous carbon catalyst.
2. The method for synthesizing ammonia using a Co-supported porous carbon catalyst based on heavy bio-oil according to claim 1, wherein the Co-supported porous carbon catalyst is added to a plasma-assisted ammonia synthesis reactor, and N 2 and H 2 are fed to the plasma-assisted ammonia synthesis reactor to react the ammonia.
3. The method for synthesizing ammonia using a Co-supported porous carbon catalyst based on heavy bio-oil according to claim 1, wherein the temperature of ammonia synthesis is 200-400 ℃.
4. The method of synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein N 2 and H 2 are fed into the plasma-assisted ammonia synthesis reactor at a flow rate of 1:7 to 7:1 ratio.
5. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein in the step (1), the Co source is Co (NO 3)2·6H2O,Co(NO3)2·6H2 O to heavy bio-oil mass ratio is 1:10-20.
6. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein in the step (2), the pre-carbonization is performed under an inert gas atmosphere by raising the temperature to 500 to 550 ℃ at a rate of 5 to 10 ℃/min and maintaining for 1 to 1.5 hours.
7. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein in the step (3), the base is NaOH and the NaOH is added in an amount 1 to 3 times the mass of the powder B.
8. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein in the step (3), the condition of carbonization is that the temperature is raised to 800 to 850 ℃ at a rate of 5 to 10 ℃/min under an inert gas atmosphere and maintained for 2 to 2.5 hours.
9. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 1, wherein in step (3), the powder C is washed several times with an acid solution and water, respectively, salts and impurities in the powder C are removed, and the obtained product is dried to obtain the Co-supported porous carbon catalyst.
10. The method for synthesizing ammonia using a heavy bio-oil based Co-supported porous carbon catalyst according to claim 8, wherein in the step (4), the acid solution is HCl solution.
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