CN115025801A - Nitrogen-doped carbon-supported CoMoS catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-supported CoMoS catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly discloses a nitrogen-doped carbon-supported CoMoS catalyst, which is prepared by the following steps: adding a carbon source, a nitrogen source and a template agent into a ball milling tank, adding ethanol as a control agent, and carrying out ball milling to obtain solid powder, N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating the substrate in the atmosphere,grinding to prepare porous NDC; adding a surfactant and cyclohexane into a round-bottom flask, adding an S precursor, dropwise adding a mixed solution of Co and Mo precursors, and magnetically stirring to obtain a mixed solution; adding into porous NDC, magnetically stirring, evaporating to remove cyclohexane to obtain solid, grinding, and adding N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating in the atmosphere, and grinding to obtain the CoMoS/NDC catalyst. The method is simple to operate, energy-saving and efficient, and solves the problems of low yield, complex product extraction difficulty and the like of the traditional coal-based aromatic hydrocarbon.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a nitrogen-doped carbon-supported CoMoS catalyst, and a preparation method and application thereof.
Background
The method for preparing the chemical by using the coal can effectively relieve the dependence of China on imported crude oil, can reduce the pollution influence of the coal as basic energy on the environment, and is a main realization path of the aim of clean and efficient utilization of the coal in the future. The liquid products derived from direct coal liquefaction, gasification or coking are rich in phenolic compounds, mainly alkylphenol compounds. Phenolic compounds are important raw materials for synthetic plastics, phenolic resins, bisphenol A, rayon, polyphenylene oxide, caprolactam and other chemical products. Due to the diversity and position uncertainty of oxygen-containing groups on the aromatic ring, coal derived alkylphenol compounds have numerous isomers, complex compositions, difficult separation of single alkylphenol products and high energy consumption and economic cost. Through catalytic hydrodeoxygenation, alkylphenol can be converted into light aromatic hydrocarbons with simpler components such as benzene, toluene, xylene, trimethylbenzene and the like, and a light aromatic hydrocarbon product is hopefully obtained through subsequent fine separation. For example, 3 isomers of cresol (ortho, meta and para-cresol) are catalytically hydrodeoxygenated to produce toluene, and xylenol (containing 6 isomers) is catalytically hydrodeoxygenated to produce 3 xylene isomers. Therefore, how to reduce the hydrogen consumption and improve the activity and selectivity of the catalyst to the maximum has important significance on the Hydrodeoxygenation (HDO) of the coal-derived phenols.
Among the different oxygen-containing groups on the aromatic ring, the phenolic hydroxyl oxygen is one of the more difficult to remove because the C-O-sigma bond is connected to the aromatic ring, and the bond energy is very difficult to remove. Research shows that two parallel reaction routes exist in HDO of phenol, namely Direct Deoxidation (DDO) accompanied by direct breakage of aromatic C-O bonds to generate aromatic hydrocarbon; the other is hydro-dehydration (HYD), which is a reaction in which a benzene ring is hydrogenated first and then dehydrated. The first removal route minimizes H 2 Consumption and energy consumption saving. Currently, catalysts for phenolic HDO include metal sulfides, non-noble metals/oxides, noble metals, and metallic carbon/nitrogen/phosphides. The metal sulfide catalyst is a phenol hydrodeoxygenation catalyst which is most reported at present due to low price, easy obtaining, high activity and high selectivity, and is carried out according to a DDO reaction route in the hydrodeoxygenation process, so that H is greatly reduced 2 And (4) consumption. Relevant studies found that the CoMoS catalyst showed higher activity and selectivity in HDO of phenols than the NiMoS catalyst. Therefore, the CoMoS catalyst can effectively remove oxygen-containing groups in phenols and minimize hydrogen energy consumption.
The combination form of the active components, the type of the carrier and the like are important factors influencing the hydrodeoxygenation activity and selectivity of the CoMoS catalyst. Research shows that the activated carbon supported CoMoS catalyst can selectively catalyze the hydrodeoxygenation of lignin-derived phenols to obtain aromatic hydrocarbons with high yield (Applied Catalysis A: General, 2020, 606: 117811.). Nitrogen doping is an important strategy to improve the surface and physicochemical properties of activated carbon, thereby improving the activity and stability of the catalyst, and the like. As an electron donor, nitrogen atoms in porous nitrogen-doped carbon (NDC) play a certain role in reducing metals; the local electron transfer function between the metal and the NDC can enhance the binding force between the metal and the NDC as a carrier, increase the active sites of the catalyst, improve the sintering resistance and oxidation resistance of the catalyst, and is a catalyst carrier which is more excellent than active carbon. Therefore, the porous NDC supported CoMoS catalyst is expected to show good activity, selectivity and stability in the preparation of aromatic hydrocarbon by catalytic hydrodeoxygenation of coal-derived phenols.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a CoMoS/NDC catalyst for preparing aromatic hydrocarbon by hydrodeoxygenation of lignite-derived phenols and a process for preparing aromatic hydrocarbon by directional conversion of coal-derived phenols. The method is simple to operate, energy-saving and efficient, and solves the problems of low yield, complex product extraction difficulty and the like of the traditional coal-based aromatic hydrocarbon.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a nitrogen-doped carbon-supported CoMoS catalyst comprises the following steps:
1) adding a carbon source, a nitrogen source and a template agent into a ball milling tank, adding ethanol as a control agent, and carrying out ball milling to obtain solid powder;
2) putting the solid powder obtained in the step 1) into a porcelain boat, N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating in an atmosphere, taking out a solid, and grinding to prepare porous NDC;
3) adding a surfactant and cyclohexane into a round-bottom flask, adding an S precursor, dropwise adding a mixed solution of a Co precursor and a Mo precursor, and magnetically stirring to obtain a mixed solution;
4) adding the porous NDC obtained in the step 2) into the mixed solution obtained in the step 3), magnetically stirring, and evaporating cyclohexane to obtain a solid;
5) grinding the solid obtained in the step 4), and putting the ground solid into a porcelain boat, N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating in the atmosphere, taking out and grinding to obtain the CoMoS/NDC catalyst.
Further, in the step 1), the template agent is a mixture of potassium chloride and zinc chloride in a mass ratio of 1 (0-2), the carbon source is one of lignin, glucose, glucosamine salt or activated carbon, the nitrogen source is one of melamine, dicyanodiamine or urea, and the mass ratio of the carbon source to the nitrogen source is 1: (0-1.5), wherein the mass ratio of the carbon source to the template agent is 1: (5-15), wherein the mass-to-liquid ratio of the carbon source to the ethanol is 1 g: (1-3) mL.
Further, in the step 2), the calcining temperature is 500-900 ℃; in the step 5), the calcining temperature is 400-800 ℃.
Further, in the step 3), the surfactant is Brij30, and the volume ratio of Brij30 to cyclohexane is 1: (5-50), the S precursor is ammonium sulfide, the Co precursor is cobalt nitrate hexahydrate, the Mo precursor is ammonium heptamolybdate, the molar ratio of Co element, Mo element and S element in the cobalt nitrate hexahydrate, the ammonium heptamolybdate and the ammonium sulfide is 1 (0-1): 0.1-0.50, the ratio of Brij30 to Co element is 1 mL: (0.005-0.05) mol.
Further, in the step 3), the magnetic stirring time is 2-12 hours; in the step 4), the magnetic stirring time is 1-4 h.
Further, in the step 1), the ball milling is performed for 1-4 hours at a rotation speed of 400-800 rpm/min by using a ball mill; in the step 2) and the step 5), the heating rate is 2-10 ℃/min, the calcining heat preservation time is 2-6 h, the passivation time is 0.5-2 h, and the grinding refers to grinding to 60-200 meshes.
The invention also provides a nitrogen-doped carbon-supported CoMoS catalyst prepared by the preparation method.
The invention also provides an application of the nitrogen-doped carbon-loaded CoMoS catalyst in catalytic hydrodeoxygenation of coal-derived phenols, which comprises the following steps: adding 50 mg of nitrogen-doped carbon-supported CoMoS catalyst, 1 mmol of phenolic compound and 20mL of solvent into a magnetic stirring high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 1-4 MPa of hydrogen, reacting at 250-300 ℃ for 2-24 h, cooling the reaction kettle after the reaction is finished, releasing pressure, taking out upper-layer liquid, and performing qualitative and quantitative analysis by GC-MS and GC.
Further, the phenolic compound is one of phenol, alkylphenol, methoxyphenol, alkylmethoxyphenol, naphthol, methylnaphthol, or coal-derived mixed phenol, and the solvent is one of methanol, ethanol, n-hexane, cyclohexane, or 1, 4-dioxane.
Has the advantages that:
the nitrogen-doped carbon-loaded CoMoS catalyst provided by the invention has high activity and high selectivity for phenol hydrodeoxygenation, the preparation process is simple to operate, energy-saving and efficient, coking and hydrogenation reduction steps caused by high-temperature calcination in the traditional catalyst preparation process are avoided, and the energy consumption and the preparation cost of the catalyst are reduced; the prepared CoMoS catalyst has stable property at high temperature and high pressure, is not easy to inactivate, has good cycle performance and has stronger sintering resistance; through catalytic hydrodeoxygenation of the lignite-derived phenolic compound, the yield of aromatic hydrocarbon is higher than 50%, the selectivity is higher than 80%, and the problems of low yield, complex extraction difficulty of products and the like of the traditional coal-derived aromatic hydrocarbon are solved.
Drawings
Fig. 1 is an SEM image of a nitrogen-doped carbon-supported CoMoS catalyst according to the present invention;
fig. 2 is a TEM image of a nitrogen doped carbon supported CoMoS catalyst according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
Example 1
1) A preparation method of a nitrogen-doped carbon-loaded CoMoS catalyst comprises the steps of weighing 1g of activated carbon as a carbon source, 1.2 g of melamine as a nitrogen source, 4 g of potassium chloride and 6 g of zinc chloride as template agents, adding the mixture into a ball milling tank, adding 1 mL of ethanol as a control agent, and then ball milling for 2 hours at a rotation speed of 600 rpm/min by using a ball mill.
2) Putting the solid powder obtained in the step 1) into a porcelain boat, N 2 Heating to a specified temperature in a tubular furnace at a heating rate of 5 ℃/min under the atmosphere, calcining, keeping the temperature for 2 hours, cooling to room temperature, and continuing to perform reaction in N 2 Passivating for 0.5 h under the atmosphere. And taking out the obtained solid, and grinding the solid to 60-200 meshes by using an agate mortar to prepare the porous NDC.
3) 0.5 mL of surfactant Brij30 and 10 mL of cyclohexane are added into a round-bottom flask, the volume ratio of the surfactant to the cyclohexane is 1:20, a certain amount of S precursor ammonium sulfide is added, the mixed solution of Co precursor cobalt nitrate hexahydrate and Mo precursor ammonium heptamolybdate is dropwise added into the round-bottom flask, the Co element, the Mo element and the S element are respectively 0.0025 mol, 0.0025 mol and 0.00075 mol, and the mixture is magnetically stirred at room temperature for 4 hours.
4) Adding the porous NDC obtained in the step 2) into the mixed solution obtained in the step 3), magnetically stirring at room temperature for 1 h, and evaporating cyclohexane to obtain a solid.
5) Grinding the solid obtained in the step 4) to 60-200 meshes, putting the ground solid into a porcelain boat, and adding N 2 Heating to 550 ℃ in a tube furnace at the heating rate of 5 ℃/min in the atmosphere, calcining and preserving heat for 4 hours, cooling, and continuing to perform reaction in N 2 Passivating for 0.5 h in the atmosphere, taking out and grinding to 60-200 meshes to obtain the CoMoS/NDC catalyst. Partial characterization of the catalyst is shown in figures 1 and 2.
Fig. 1 is an SEM image of a nitrogen-doped carbon-supported CoMoS catalyst, and fig. 1 shows that the sulfide phase of the CoMoS/NDC catalyst exhibits a flower-like morphology.
FIG. 2 is a TEM image of a nitrogen-doped carbon-supported CoMoS catalyst, and FIG. 2 shows that the active component of the CoMoS/NDC catalyst is uniformly dispersed on the surface of a carrier and presents lattice stripes with different crystal planes.
Weighing 50 mg of the CoMoS/NDC catalyst, 1 mmol of phenolic compound and 20mL of cyclohexane, adding the mixture into a 100 mL high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 2 MPa of hydrogen, reacting at 300 ℃ for 6 hours, cooling the reaction kettle to room temperature after the reaction is finished, releasing pressure, taking out upper-layer liquid, and performing qualitative and quantitative analysis by using GC-MS and GC. The results of catalytic hydrodeoxygenation of a portion of the phenolic compounds are shown in table 1. The result shows that the CoMoS/NDC catalyst has good hydrodeoxygenation activity to alkylphenol compounds, can generate aromatic hydrocarbon with high selectivity, and the aromatic hydrocarbon selectivity is higher than 80%.
TABLE 1 CoMoS/NDC catalyzed hydrodeoxygenation of alkylphenols to alkylbenzenes
Example 2
Effect of calcination temperature of different NDC supports on hydrodeoxygenation of coal-derived phenols. Weighing 50 mg of the CoMoS/NDC catalyst prepared by the preparation method, 1 mmol of p-cresol and 20mL of cyclohexane, adding the catalyst into a 100 mL high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 2 MPa of hydrogen, reacting for 6h at 300 ℃, cooling the reaction kettle to room temperature after the reaction is finished, releasing pressure, taking out upper-layer liquid, and carrying out qualitative and quantitative analysis by using GC-MS and GC. The result shows that the CoMoS/NDC catalyst has good catalytic hydrodeoxygenation effect on phenols at 300 ℃, and the effect is optimal when the NDC calcination temperature is 700 ℃.
In the step, the calcination temperature of the CoMoS/NDC is 550 ℃, and the volume ratio of the surfactant to the cyclohexane is 1:20, the molar ratio of the Co element, the Mo element and the S element is 1: 1: 0.3.
Example 3
Effect of volume ratio of different surfactants to cyclohexane on hydrodeoxygenation of coal derived phenols. Weighing 50 mg of the CoMoS/NDC catalyst prepared by the preparation method, 1 mmol of p-cresol and 20mL of cyclohexane, adding the catalyst into a 100 mL high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 2 MPa of hydrogen, reacting for 6h at 300 ℃, cooling the reaction kettle to room temperature after the reaction is finished, releasing pressure, taking out upper-layer liquid, and carrying out qualitative and quantitative analysis by using GC-MS and GC. The result shows that the CoMoS/NDC catalyst has good catalytic hydrodeoxygenation effect on phenols at 300 ℃, and the volume ratio of the surfactant to cyclohexane is 1: the best effect is obtained after 20 days.
In the step, the NDC calcination temperature is 700 ℃, the CoMoS/NDC calcination temperature is 550 ℃, and the molar ratio of Co element, Mo element and S element is 1: 1: 0.3.
Example 4
Effect of calcination temperatures of different CoMoS/NDC on hydrodeoxygenation of coal-derived phenols. Weighing 50 mg of the CoMoS/NDC catalyst prepared by the preparation method, 1 mmol of p-cresol and 20mL of cyclohexane, adding the catalyst into a 100 mL high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 2 MPa of hydrogen, reacting for 6h at 300 ℃, cooling the reaction kettle to room temperature after the reaction is finished, releasing pressure, taking out upper-layer liquid, and carrying out qualitative and quantitative analysis by using GC-MS and GC. The results show that the CoMoS/NDC catalyst has good catalytic hydrodeoxygenation effect on phenols at 300 ℃, and the best condition of the CoMoS/NDC catalyst is that the calcination temperature is 550 ℃.
In the step, the NDC calcination temperature is 700 ℃, and the volume ratio of the surfactant to the cyclohexane is 1:20, the molar ratio of the Co element, the Mo element and the S element is 1: 1: 0.3.
The protection content of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be protected by the following claims.
Claims (10)
1. A preparation method of a nitrogen-doped carbon-supported CoMoS catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) adding a carbon source, a nitrogen source and a template agent into a ball milling tank, adding ethanol as a control agent, and carrying out ball milling to obtain solid powder;
2) putting the solid powder obtained in the step 1) into a porcelain boat, N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating in an atmosphere, taking out a solid, and grinding to prepare porous NDC;
3) adding a surfactant and cyclohexane into a round-bottom flask, adding an S precursor, dropwise adding a mixed solution of a Co precursor and a Mo precursor, and magnetically stirring to obtain a mixed solution;
4) adding the porous NDC obtained in the step 2) into the mixed solution obtained in the step 3), magnetically stirring, and evaporating cyclohexane to obtain a solid;
5) grinding the solid obtained in the step 4), putting the ground solid into a porcelain boat, and N 2 Heating in atmosphere, calcining, cooling, and continuously adding N 2 Passivating in the atmosphere, taking out and grinding to obtain the CoMoS/NDC catalyst.
2. The method of claim 1, wherein the nitrogen-doped carbon-supported CoMoS catalyst is prepared by the following steps: in the step 1), the template agent is a mixture of potassium chloride and zinc chloride in a mass ratio of 1 (0-2), the carbon source is one of lignin, glucose, glucosamine salt or activated carbon, the nitrogen source is one of melamine, dicyanodiamine or urea, and the mass ratio of the carbon source to the nitrogen source is 1: (0-1.5), wherein the mass ratio of the carbon source to the template agent is 1: (5-15), wherein the mass-to-liquid ratio of the carbon source to the ethanol is 1 g: (1-3) mL.
3. The method of claim 1, wherein the nitrogen-doped carbon-supported CoMoS catalyst is prepared by the following steps: in the step 2), the calcining temperature is 500-900 ℃; in the step 5), the calcining temperature is 400-800 ℃.
4. The method of claim 1, wherein the method comprises the following steps: in the step 3), the surfactant is Brij30, and the volume ratio of Brij30 to cyclohexane is 1: (5-50), the S precursor is ammonium sulfide, the Co precursor is cobalt nitrate hexahydrate, the Mo precursor is ammonium heptamolybdate, the molar ratio of Co elements, Mo elements and S elements in the cobalt nitrate hexahydrate, the ammonium heptamolybdate and the ammonium sulfide is 1 (0-1): 0.1-0.50, and the ratio of Brij30 to Co elements is 1 mL: (0.005-0.05) mol.
5. The method of claim 1, wherein the nitrogen-doped carbon-supported CoMoS catalyst is prepared by the following steps: in the step 3), the magnetic stirring time is 2-12 h; in the step 4), the magnetic stirring time is 1-4 h.
6. The method of claim 1, wherein the nitrogen-doped carbon-supported CoMoS catalyst is prepared by the following steps: in the step 1), ball milling is performed for 1-4 hours at a rotating speed of 400-800 rpm/min by using a ball mill; in the step 2) and the step 5), the heating rate is 2-10 ℃/min, the calcining heat preservation time is 2-6 h, the passivation time is 0.5-2 h, and the grinding refers to grinding to 60-200 meshes.
7. The nitrogen-doped carbon-supported CoMoS catalyst prepared by the preparation method of any one of claims 1 to 6.
8. Use of the nitrogen-doped carbon-supported CoMoS catalyst of claim 7 in catalytic hydrodeoxygenation of coal-derived phenols.
9. The use of the nitrogen-doped carbon-supported CoMoS catalyst of claim 8 in the catalytic hydrodeoxygenation of coal-derived phenols, wherein: the method comprises the following steps: adding 50 mg of nitrogen-doped carbon-supported CoMoS catalyst, 1 mmol of phenolic compound and 20mL of solvent into a magnetic stirring high-pressure reaction kettle, replacing air with nitrogen for 3 times, filling 1-4 MPa of hydrogen, reacting at the temperature of 250-300 ℃ for 2-24 h, cooling the reaction kettle after the reaction is finished, releasing pressure, taking out upper-layer liquid, and performing qualitative and quantitative analysis by using GC-MS and GC.
10. The use of a nitrogen-doped carbon-supported CoMoS catalyst according to claim 9 in the catalytic hydrodeoxygenation of coal-derived phenols, wherein: the phenolic compound is one of phenol, alkylphenol, methoxyphenol, alkyl methoxyphenol, naphthol, methyl naphthol or coal-derived mixed phenol, and the solvent is one of methanol, ethanol, n-hexane, cyclohexane or 1, 4-dioxane.
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