CN114478198B - Method for preparing phenol by catalytic hydrogenation of guaiacol - Google Patents
Method for preparing phenol by catalytic hydrogenation of guaiacol Download PDFInfo
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Abstract
The invention belongs to the technical field of phenol preparation, and discloses a method for preparing phenol by catalytic hydrogenation of guaiacol, namely, guaiacol is subjected to selective hydrogenation reaction under the action of a CoFe bimetallic and reduced graphene oxide rGO composite material catalyst to generate phenol. The CoFe/rGO catalyst does not need to be subjected to high-temperature pre-reduction treatment before use, and reacts for 3 hours under the conditions of 300 ℃ and 1MPa of hydrogen pressure, the conversion rate of guaiacol can reach 94%, and the selectivity of phenol is 70.8%. And the CoFe/rGO catalyst without reduction pretreatment is cheaper than noble metal catalysts such as Pt, pd and the like, and has industrial application value.
Description
Technical Field
The invention belongs to the technical field of phenol preparation, relates to a method for preparing phenol by catalytic hydrogenation of guaiacol, and in particular relates to a cobalt-iron bimetallic-reduced graphene oxide catalyst CoFe/rGO, a preparation method of the catalyst and application of the catalyst in preparing phenol.
Background
With the development of society, great pressure is brought to natural environment by great consumption of energy, and it is urgent to find new energy which can replace fossil fuel and reduce environmental pollution. Biomass energy is a novel renewable clean energy source, and is mainly composed of C, H, O and other elements because the biomass energy is similar to fossil fuel in composition, so that the biomass energy is expected to become a traditional fossil fuel substitute and is used for continuously supplying hydrocarbon resources for human beings. Wherein lignin accounts for 30-40% of the mass of biomass, is a sufficient renewable raw material, and lignin biomass chemical conversion reaction is widely paid attention to domestic and foreign students in recent years.
Guaiacol (GUA) is the most typical model compound of lignin, and its chemical structure contains hydroxyl and methoxy groups, which are widely present in lignin polymers, so that a large number of researchers have generally chosen to conduct hydrodeoxygenation reaction studies. Under the action of a catalyst, the guaiacol can obtain Phenol (Phenols) through hydrodeoxygenation reaction. Phenol is a very important bulk chemical raw material and intermediate in the chemical industry, and is important in fine chemical industry and oil refining industry, such as: the method can be used for synthesizing phenolic resin to prepare high-temperature-resistant and corrosion-resistant materials; the synthetic caprolactam is used for the production and manufacture of artificial synthetic fibers and artificial leather; the synthesis of acetylsalicylic acid to make aspirin is used in the pharmaceutical industry, and thus phenol is very widely used.
Currently, catalysts used in this field mainly include noble metal catalysts (Ru/C, pd/C, pt/C) and non-noble metal catalysts, such as cobalt-based catalysts (Co/rGO, niCo/gamma-Al 2 O 3 ) Nickel-based catalyst (Ni/Al) 2 O 3 Ni/C), molybdenum-based catalyst (Mo 2 C/CNT、MoS 2 and/C) and the like. Although some precious metal catalysts have been able to achieve better catalytic results so far, some researchers have focused on non-precious metal catalysts due to their expensive price and limited use on a large scale. Simone, ansalon, nunzio, et al, hydroodeoxycogenation ofguaiacol over molybdenum-based catalysts The effect of support and the nature of the active site [ J]The Canadian Journal of Chemical Engineering,2017,95 (9): 1730-1744 et al tested several Mo-based catalysts (SiO) in a batch reactor 2 、Al 2 O 3 NaY zeolite, mgO, activated carbon and graphite as carrier) on guaiacol, it was found that at 350℃4MPa H 2 Mo showed the best performance on activated carbon for guaiacol demethoxy, the reaction was completely converted, and the selectivity to phenol was 72%. Cai Z, wang F, zhang X, et al, selective hydrogen oxidationnation ofguaiacol to phenolics over activated carbon supported molybdenum catalysts[J]Molecular Catalysis,2017,441:28-34 et al H 2 The Mo catalyst loaded by the active carbon is prepared by reduction, and the temperature is 300 ℃ and the pressure is 3MPa H 2 It catalyzes the HDO reaction of guaiacol under pressure. The detected main product is phenol, the yield of phenol reaches 70%, and experiments show that the low temperature is favorable for selectively generating the phenol product, and compared with hydrocarbon solvents, the tetralin and decalin solvents are more favorable for reaction. However, from the above experiments, it was found that the catalyst was reduced for the Mo-based catalyst, which consumed a large amount of H 2 Not beneficial to saving energy. In addition, the catalyst needs pre-reduction treatment, which not only complicates the catalyst preparation and maintenance process and increases energy consumption, but also some reduced catalysts may lose activity due to oxidation.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a transition metal and graphene composite CoFe/rGO catalyst and a method for preparing phenol by catalyzing and hydrogenating guaiacol by using the same.
The invention is characterized in that: the catalyst takes cheap transition metal Co as a hydrogenation active component, takes transition metal Fe as an auxiliary agent and reduced graphene oxide rGO as a carrier, and the prepared catalyst can be used for catalyzing the reaction of preparing phenol by hydrogenating guaiacol without high-temperature pre-reduction treatment. The synthesized catalyst does not need reduction pretreatment, and generates higher catalytic activity and product selectivity under mild conditions, thereby providing a novel high-efficiency catalyst for preparing phenol by selective hydrogenation of guaiacol.
The aim of the invention is realized by the following technical scheme:
a method for preparing phenol by catalytic hydrogenation of guaiacol, comprising the following steps: n-dodecane is used as a solvent, and guaiacol reacts with H under the action of CoFe/rGO catalyst 2 The reaction is carried out at 260-320 ℃ and 0.5-3 MPa for 0.5-4h to obtain phenol.
Furthermore, the method for preparing phenol by hydrogenation of guaiacol adopts an intermittent kettle reaction, and comprises the following specific steps:
(1) And (3) loading: taking a mechanically-stirred high-pressure reaction kettle, adding guaiacol, n-dodecane serving as a solvent, tetradecane serving as an internal standard and CoFe/rGO serving as a catalyst, screwing the reaction kettle, checking the air tightness of the device, ensuring that the device is airtight, and then introducing 1MPaH 2 ；
(2) The reaction: setting the heating temperature of the reaction kettle at 300 ℃, reacting for 3 hours, stirring at 500-800RPM, and starting an experiment;
(3) Analysis of results: after the reaction is finished, collecting gas phase and liquid phase products, analyzing by gas chromatography, and recovering the catalyst by centrifugation;
the prepared CoFe/rGO catalyst does not need reduction pretreatment before being added into a reaction kettle.
Further, the dosage of the CoFe/rGO catalyst is 10-80% of the mass of the guaiacol.
The CoFe/rGO catalyst has the following composition and preparation process:
the active metal of the catalyst for providing hydrogenation catalysis function is Co, and the metal for assisting and adjusting the selectivity of the product is Fe; the carrier of the catalyst is reduced graphene oxide rGO.
The catalyst is prepared by adopting a dipping-roasting method, and comprises the following specific steps:
(1) Preparation of a graphene carrier: 230mL of concentrated sulfuric acid and 5.0g of NaNO were taken 3 Adding 10g of natural crystalline flake graphite powder under stirring, stirring for 2.5h, and adding 30g of KMnO 4 Transferring to 35 ℃ constant temperature water bath for reaction for 2h, adding 460mL of deionized water, stirring for 15min in 98 ℃ oil bath, and finally adding 1.4L of deionized water to terminate the reaction, and simultaneously adding 25mL of 30% H 2 O 2 Cooling to room temperature, centrifugally washing with deionized water, washing to neutrality, dispersing the prepared GO paste with the dry basis content of 1g in 1000mL of deionized water, carrying out ultrasonic treatment for 30min, standing and aging, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing in an oil bath at 95 ℃ for 3h, adding 4mL of 80% hydrazine hydrate for reaction for 30min, adding 4% hydrochloric acid solution, carrying out suction filtration while hot, and freeze-drying to obtain an rGO carrier for standby;
(2) Preparation of salt solution: taking a certain amount ofCo(NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·9H 2 O is mixed and dissolved in a beaker by deionized water and ethanol to prepare a salt solution;
(3) Dipping: weighing a corresponding amount of rGO, adding the rGO into the solution prepared in the step (2), continuously stirring the solution by using a glass rod, and standing the sample at room temperature for about 3 hours;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12 hours, and grinding the sample into powder by an agate mortar;
(5) Roasting: and (3) placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by a program of 10 ℃/min under the nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, and taking out the sample and storing the sample in a sealing way when the temperature is reduced to the room temperature.
Co (NO) in the step (2) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·9H 2 The mass ratio relation of O is 1:0.2-1:0.5, and 1 is preferably adopted: 0.35, and Co (NO) 3 ) 2 ·6H 2 The ratio relation of O and the carrier rGO is that each g of rGO carries 2.0mmol of Co.
Compared with the prior art, the invention has the following advantages and effects:
(1) Fe auxiliary agent is introduced into the catalyst, so that the phenol selectivity is remarkably improved. The activity of the pure Co catalytic component is too high, the benzene ring is easy to saturate, the selectivity of the phenol aromatic compound is greatly reduced, and finally the cyclohexanol or cyclohexane byproducts are obtained. Fe itself has very low hydrogenation activity on guaiacol. However, the introduction of Fe into Co passivates Co hydrogenation activity to some extent, allowing the reaction to remain in the phenol step.
(2) Graphene is introduced into the catalyst, and Fe plays an electronic regulation and control role on Co by means of the graphene. Graphene is a polycyclic large aromatic molecule, the planar structure contains rich pi-electrons and has good conductive property, so Co and Fe atoms distributed on the crystal face of the graphene generate an electron synergistic effect by taking the graphene as a bridge, thereby improving the phenol selectivity and the catalyst activity
(3) Co and Fe are non-noble metals, the cost is low, and in addition, the CoFe/rGO catalyst does not need to be subjected to high-temperature pre-reduction treatment and cannot be deactivated due to oxidation. The catalyst does not need pre-reduction treatment, so that the preparation and maintenance processes of the catalyst are greatly simplified, the energy consumption is reduced, and the catalyst does not worry about the loss of activity due to oxidation in the use process.
(4) The CoFe/rGO catalyst is prepared by adopting an impregnation-roasting method, and the preparation method is simple and is suitable for large-scale industrialized preparation. Compared with Co/rGO catalyst, under the regulation and control of Fe, the CoFe/rGO catalyst selectively hydrogenates carbonyl and hydroxyl carbon-oxygen bonds, obviously reduces hydrogenation of carbon-carbon bonds of benzene rings, and reduces hydrogenation rate of 1MPaH at 300 DEG C 2 Under the condition of 3 hours, the yield of the phenol can reach 66.6 percent, and the high selectivity of the phenol is reflected.
In conclusion, when the CoFe/rGO catalyst is used for catalyzing the hydrogenation reaction of guaiacol, the reaction has the characteristics of high reaction activity, high selectivity and the like, the conversion rate of guaiacol can reach 94%, the phenol selectivity can reach 70.8%, the catalyst does not need to be subjected to high-temperature prereduction in the reaction process, and the preparation method is suitable for industrialized mass preparation and has obvious advantages and industrial application value.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and all experimental equipment, materials, reagents and the like used can be purchased from chemical companies.
Graphene is introduced into the catalyst, so that the graphene not only plays a role of a carrier, but also can modulate the electronic characteristics of the metal active component, and the catalyst has excellent catalytic performance. KUMAR Sulender, KUMAR Divyararan, KISHORE Brij, et al, electrochemical investigations ofCo 3 Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media[J]Co was studied by chronovoltammetry, applied Surface Science,2017,418:79-86 3 Fe and Co 3 Fe-RGO catalyst, found graphene and Co 3 The strong electron synergism between Fe can protect Co 3 Fe noOxidized and corroded. Co as a non-noble metal catalyst 3 Fe-rGO has strong alkali liquor tolerance when being used for Oxygen Reduction Reaction (ORR). Graphene is a polycyclic large aromatic molecule, and the planar structure contains rich pi-electrons and has good conductive characteristics, so that the graphene serving as a carrier not only can provide a large specific surface area, but also can form a strong electron synergistic effect with active components such as loaded metal, metal oxide and the like, and the performance of the catalyst is improved.
The method for constructing the catalyst by combining Co, fe and graphene is an innovation of the invention. For the hydrogenation of guaiacol, a typical reaction path is that guaiacol is first hydrogenated to phenol, phenol is further hydrogenated to cyclohexanol, which if hydrogenated is continued, then cyclohexane is formed. Firstly, fe auxiliary agent is introduced into the catalyst, so that the phenol selectivity is remarkably improved. The pure Co catalytic component has high activity, is easy to saturate benzene ring, greatly reduces the selectivity of phenol aromatic compounds, and finally obtains cyclohexanol or cyclohexane byproducts, and the details are shown in comparative example 1.Fe itself has very low hydrogenation activity on guaiacol, as shown in comparative example 2. However, the introduction of Fe into Co passivates Co hydrogenation activity to some extent, allowing the reaction to remain in the phenol step. Secondly, graphene is introduced into the catalyst, and Fe plays an electronic regulation and control role on Co by means of the graphene. Graphene is a polycyclic large aromatic molecule, and the planar structure contains rich pi-electrons and has good conductive characteristics, so that Co and Fe atoms distributed on the crystal face of the graphene generate an electron synergistic effect by taking the graphene as a bridge, thereby improving the phenol selectivity and the catalyst activity. When the same method is adopted and HY zeolite molecular sieve is used as a carrier, the prepared CoFe/HY catalyst cannot show similar catalytic performance, and the details are shown in comparative example 3.
Examples 1 to 4 batch reactions at different reaction temperatures
1. And (3) preparing a catalyst: the preparation method of the CoFe/rGO catalyst by adopting the dipping-roasting method comprises the following specific steps:
(1) Preparation of a graphene carrier: 230mL of concentrated sulfuric acid and 5.0g of NaNO were taken 3 Stirring, adding 10g of natural crystalline flake graphite powder, stirringAdding KMnO after stirring for 2.5h 4 Transferring to 35 ℃ constant temperature water bath for reaction for 2h, adding 460mL of deionized water, stirring for 15min in 98 ℃ oil bath, and finally adding 1.4L of deionized water to terminate the reaction, and simultaneously adding 25mL of 30% H 2 O 2 Cooling to room temperature, centrifugally washing with deionized water, washing to neutrality, dispersing the prepared GO paste with the dry basis of 1g in 1000mL of deionized water, carrying out ultrasonic treatment for 30min, standing and aging, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing in an oil bath at 95 ℃ for 3h, adding 4mL of 80% hydrazine hydrate for reaction for 30min, adding 4% hydrochloric acid solution, carrying out suction filtration while hot, and freeze-drying to obtain the rGO carrier for standby.
(2) Preparation of salt solution: 58.2mg of Co (NO) 3 ) 2 ·6H 2 O and 28.3mgFe (NO) 3 ) 2 ·9H 2 O, dissolving with 0.82mL of deionized water and 0.2mL of absolute ethyl alcohol to prepare a salt solution;
(3) Dipping: the prepared salt solution was placed in a beaker, 100mg of rGO was weighed, added to the beaker, and stirring was continued with a glass rod. Standing the sample at room temperature for 3 hours;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12 hours, and grinding the sample into powder by an agate mortar;
(5) Roasting: placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by a program of 10 ℃/min under nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, cooling the quartz tube to room temperature, taking out the quartz tube, and sealing and storing the quartz tube;
2. reaction test: the performance of the CoFe/rGO catalyst for catalyzing the guaiacol hydrogenation reaction is tested by adopting intermittent reaction, and the method comprises the following specific steps:
(1) Taking a mechanically-stirred high-pressure reaction kettle, adding 300.0mg of guaiacol, 10ml of n-dodecane, 120mg of internal standard substance tetradecane and 30mg of CoFe/rGO catalyst into the high-pressure reaction kettle, screwing the reaction kettle, checking the air tightness of the device, ensuring the device to be airtight, and then introducing 1MPaH 2 The stirring rate was 700rpm, and the designated temperature was set for 3 hours.
(2) After the reaction, the liquid phase product was collected and analyzed by gas chromatography. The catalyst was recovered by centrifugation.
Wherein: conversion of guaiacol= (amount of guaiacol substance at the beginning of reaction-amount of guaiacol substance at the end of reaction)/amount of guaiacol substance at the beginning of reaction x 100%
Yield of phenol = amount of phenol species at the end of the reaction/amount of guaiacol species at the start of the reaction x 100%
Phenol selectivity = yield of phenol/conversion of guaiacol x 100%
The chromatographic conditions were: the hydrogen flame detector FID is adopted, hydrogen is used as carrier gas, an internal standard method is adopted, and tetradecane is used as an internal standard.
3. The reaction results are shown in Table 1
TABLE 1 results for different reaction temperatures
Examples 1-3 show that guaiacol can also be converted at a reaction temperature of 260℃with the exception of the lower reaction rate; when the reaction temperature reaches 300 ℃, the guaiacol can achieve 94 percent conversion rate and 66.6 percent phenol yield; when the temperature is 320 ℃, the selectivity of phenol drops rapidly, and the phenol is continuously hydrogenated to cyclohexanol at high temperature. The optimal reaction temperature was 300 ℃.
Examples 3 and 5 to 7 batch reactions at different reaction pressures
1. And (3) preparing a catalyst: the procedure was as for the preparation of the catalysts in examples 1-4.
2. Reaction test: the procedure is the same as in examples 1-4 for the reaction test procedure, the specific reaction conditions: ensuring that the device is airtight and then is supplied with a specified pressure H 2 The reaction was carried out at a set temperature of 300℃for 3 hours at a stirring rate of 700 rpm.
3. The reaction results are shown in Table 2.
TABLE 2 results for different reaction pressures
Examples 3 and 5-7 show that the guaiacol conversion increases with increasing pressure when reacted for 3 hours at 0.5MPa to 3MPa and 300 ℃. When H is 2 The catalyst has better catalytic activity under the pressure of 1.0MPa, and the phenol yield can reach 66.6%; when the pressure is increased to 2.0MPa, the yield of phenol is lowered. Continue to enlarge H 2 The pressure will further hydrogenate the phenol to cyclohexanol. H of 1.0MPa 2 Is beneficial to the reaction of catalyzing guaiacol to directionally generate phenol by using a CoFe/rGO catalyst. The optimized hydrogen pressure was 1.0MPa.
Examples 3 and 8-11 batch reactions at different reaction times
1. And (3) preparing a catalyst: the procedure was as for the preparation of the catalysts in examples 1-4.
2. Reaction test: the procedure is the same as in examples 1-4 for the reaction test procedure, the specific reaction conditions: ensuring that the device is air-tight and then is introduced with 1MPaH 2 Stirring speed of 700rpm, setting temperature of 300 ℃, and reacting for a specified time.
3. The reaction results are shown in Table 3.
TABLE 3 results for different reaction times
Examples 3 and 8 to 11 can be seen at 300℃and H of 1MPa 2 When the reaction time is 1h, the guaiacol conversion rate is 74.9%, the phenol yield is 46.7%, after the reaction time reaches 3h, the phenol yield reaches 66.6%, and the reaction time is continuously prolonged, and the phenol yield starts to decrease. The phenol continues to react over time to form cyclohexanol and cyclohexane. The optimized reaction time was 3h.
Comparative example 1 batch reaction of Co/rGO catalyst
1. And (3) preparing a catalyst: the method for preparing the Co/rGO catalyst by adopting the dipping-roasting method comprises the following specific steps:
(2) Preparation of salt solution: 58.2mg of Co (NO) 3 ) 2 ·6H 2 O, preparing a salt solution by using 0.82mL of deionized water and 0.2mL of absolute ethyl alcohol;
the remaining preparation steps were the same as in examples 1-4.
2. Reaction test: the performance of the Co/rGO catalyst for catalyzing the hydrogenation reaction of guaiacol is tested by adopting batch reaction, and the specific steps are as in examples 1-4.
The reaction result shows that the guaiacol conversion rate is 100% and the phenol selectivity is 0 under the action of the catalyst. Under the condition of the same ratio, the CoFe/rGO catalyst can control the reaction in the step of phenol, and the yield of the phenol reaches 66.6 percent.
Comparative example 2 batch reaction of Fe/rGO catalyst
1. And (3) preparing a catalyst: the Fe/rGO catalyst is prepared by adopting an impregnation-roasting method, and comprises the following specific steps:
(2) Preparation of salt solution: 28.3mg of Fe (NO) 3 ) 3 ·9H 2 O, preparing a salt solution by using 0.82mL of deionized water and 0.2mL of absolute ethyl alcohol;
the remaining preparation steps were the same as in examples 1-4.
2. Reaction test: the performance of the Fe/rGO catalyst for catalyzing the guaiacol hydrogenation reaction is tested by adopting a batch reaction, and the specific steps are the same as in examples 1-4.
The reaction result shows that under the action of the catalyst, the conversion rate of the guaiacol is about 2%, and under the condition of the same ratio, the CoFe/rGO catalyst can completely convert the guaiacol, and the phenol yield reaches 66.6%.
In addition, the sum of the phenol yields obtained by the reaction of the Co/rGO catalyst and the Fe/rGO catalyst is far lower than that obtained by the reaction of the CoFe/rGO catalyst, which indicates that Co and Fe simultaneously supported on the rGO surface are not simply physically overlapped, but form a synergistic effect, and excellent catalytic effect is generated.
Comparative example 3 batch reaction of CoFe/HY catalyst
1. And (3) preparing a catalyst: the preparation method of the CoFe/HY catalyst by adopting the dipping-roasting method comprises the following specific steps:
(2) Preparation of salt solution: 582mg of Co (NO) 3 ) 2 ·6H 2 O and 283mg of Fe (NO) 3 ) 2 ·9H 2 O, dissolved in 0.82mL deionized water and 0.2mL absolute ethanolA salt solution;
(3) Dipping: the prepared salt solution was placed in a beaker, 1000mg of HY powder was weighed, added to the beaker, and stirring was continued with a glass rod. Standing the sample at room temperature for 3 hours;
the remaining preparation steps were the same as in examples 1-4.
2. Reaction test: the performance of the CoFe/HY catalyst in catalyzing the hydrogenation reaction of guaiacol was tested by batch reaction, and the specific procedure was as in examples 1-4.
The reaction results show that the guaiacol is not converted under the action of the catalyst. Under the condition of the same ratio, the CoFe/rGO catalyst can completely convert guaiacol, and the phenol yield reaches 66.6%.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The method for preparing phenol by catalytic hydrogenation of guaiacol is characterized by comprising the following steps:
(1) And (3) loading: taking a mechanically-stirred high-pressure reaction kettle, adding guaiacol, n-dodecane serving as a solvent, tetradecane serving as an internal standard and CoFe/rGO serving as a catalyst, screwing the reaction kettle, checking the air tightness of the device, ensuring that the device is airtight, and then introducing 1MPa H 2 ；
(2) The reaction: setting the heating temperature of the reaction kettle to 300 ℃, the reaction time to 3 hours, and the stirring speed to 500-800RPM, and starting an experiment;
(3) Analysis of results: after the reaction is finished, collecting gas phase and liquid phase products, analyzing by gas chromatography, and recovering the catalyst by centrifugation;
the prepared CoFe/rGO catalyst does not need reduction pretreatment before being added into a reaction kettle;
the CoFe/rGO catalyst is prepared by adopting a dipping-roasting method, and comprises the following specific steps:
(1) Preparation of a graphene carrier: taking 230mL concentrated sulfuric acid and 5.0g NaNO 3 Adding 10g natural crystalline flake graphite powder under stirring, stirring 2.5h, and adding 30g KMnO 4 Transferring to 35 ℃ constant temperature water bath for reaction 2H, adding 460mL deionized water, stirring for 15min in 98 ℃ oil bath, and finally adding 1.4L deionized water to terminate the reaction, and simultaneously adding 25ml of 30% H 2 O 2 Cooling to room temperature, centrifugally washing with deionized water, washing to neutrality, dispersing the prepared GO paste with the dry basis content of 1g in 1000mL deionized water, carrying out ultrasonic treatment for 30min, standing and aging, adding 25mL of 30% ammonia water and 6mL of 80% hydrazine hydrate, refluxing in an oil bath at 95 ℃ for 3h, adding 4mL of 80% hydrazine hydrate, reacting for 30min, adding 4% hydrochloric acid solution, filtering while hot, and freeze-drying to obtain rGO carrier for later use;
(2) Preparation of salt solution: taking a certain amount of Co (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·9H 2 O is mixed and dissolved in a beaker by deionized water and ethanol to prepare a salt solution;
(3) Dipping: weighing a corresponding amount of rGO, adding the rGO into the solution prepared in the step (2), continuously stirring the solution by using a glass rod, and standing the sample at room temperature for about 3h;
(4) And (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven, drying at 50 ℃ for 12h, and grinding the sample into powder by an agate mortar;
(5) Roasting: and (3) placing the powdery sample prepared in the step (4) into a quartz tube, placing the quartz tube into a tube furnace, heating the quartz tube to 500 ℃ from room temperature by programming at 10 ℃ per minute under nitrogen atmosphere, roasting the quartz tube at the constant temperature of 500 ℃ for 2h, and taking out the quartz tube when the temperature is reduced to room temperature, and sealing and storing the quartz tube.
2. The method for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 1, wherein the amount of the CoFe/rGO catalyst is 10-80% of the mass of guaiacol.
3. The method for preparing phenol by catalytic hydrogenation of guaiacol as set forth in claim 1, wherein said steps are as follows(2) Co (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·9H 2 The mass ratio of O is 1:0.2-1:0.5.
4. The method for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 1, wherein Co (NO 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 2 ·9H 2 The mass ratio relation of O is 1:0.35.
5. the method for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 1, wherein Co (NO 3 ) 2 ·6H 2 The ratio relation of O and the carrier rGO is that each g of rGO carries 2.0mmol of Co.
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