CN114478198A - Method for preparing phenol by catalytic hydrogenation of guaiacol - Google Patents
Method for preparing phenol by catalytic hydrogenation of guaiacol Download PDFInfo
- Publication number
- CN114478198A CN114478198A CN202210099380.3A CN202210099380A CN114478198A CN 114478198 A CN114478198 A CN 114478198A CN 202210099380 A CN202210099380 A CN 202210099380A CN 114478198 A CN114478198 A CN 114478198A
- Authority
- CN
- China
- Prior art keywords
- guaiacol
- reaction
- catalyst
- phenol
- rgo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 bimetal and reduced graphene oxide rGO composite material catalyst to generate phenol. The CoFe/rGO catalyst does not need 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%. In addition, 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, and relates to a method for preparing phenol by catalytic hydrogenation of guaiacol, in particular to a cobalt-iron bimetallic-reduced graphene oxide catalyst CoFe/rGO, a preparation method of the catalyst and application of the catalyst in preparation of phenol.
Background
With the development of society, the great consumption of energy sources brings great pressure to the natural environment, and the search for new energy sources which can replace fossil fuels and reduce the environmental pollution is urgent. The biomass energy is a novel renewable clean energy, is similar to the composition of fossil fuel, mainly comprises C, H, O and other elements, is expected to become a substitute of the traditional fossil fuel, and continuously supplies hydrocarbon resources for human beings. Wherein, the lignin accounts for 30 to 40 percent of the mass of the biomass, is an adequate renewable raw material, and in recent years, the chemical conversion reaction of lignin biomass energy is widely concerned by scholars at home and abroad.
Guaiacol (Guaiacol, GUA for short) is the most typical model compound of lignin, and the chemical structure of Guaiacol contains hydroxyl and methoxy, and these two functional groups are widely present in lignin polymers, so that extensive researchers usually choose to perform hydrodeoxygenation reaction research. In the presence of a catalyst, guaiacol can be subjected to hydrodeoxygenation reaction to obtain Phenol (Phenol). Phenol is a very important bulk chemical raw material and intermediate in the chemical industry, and is crucial in the fine chemical industry and the oil refining industry, such as: it can be used for synthesizing phenolic resin to manufacture high temperature resistant and corrosion resistant materials; the synthetic caprolactam is used for producing artificial synthetic fibers and artificial leather; the aspirin prepared by synthesizing acetylsalicylic acid is used in the pharmaceutical industry, so that the phenol has wide application.
Currently, the catalysts used in the art include primarily noble metal catalysts (Ru/C, Pd/C, Pt/C) and non-noble metal catalysts, such as cobalt-based catalysts (Co/rGO, NiCo/gamma-Al)2O3) Nickel-based catalyst (Ni/Al)2O3Ni/C), molybdenum-based catalyst (Mo)2C/CNT、MoS2and/C), etc. Although some precious metal catalysts can achieve better catalytic effect, some researchers focus on non-precious metal catalysts due to the disadvantages of high price, limitation of large-scale use and the like. Simone, Anasalon, Nunzio, et al.Hydrodeoxygenation of guaiacol over molybdenum-based analytes The effect of The report and The nature of The active site [ J]The Canadian Journal of Chemical Engineering,2017,95(9):1730-2、Al2O3NaY zeolite, MgO, activated carbon andgraphite as carrier) to guaiacol, found at 350 deg.C, 4MPa H2Mo showed the best performance on activated carbon for guaiacol demethoxylation, complete conversion and selectivity to phenol of 72%. Selected hydroxyl oxidation of guaiacol to phenolics over activated carbon n supported molybdenum catalysts [ J Z]Molecular Catalysis,2017,441:28-34, et al H2The Mo catalyst loaded by the active carbon is prepared by reduction at 300 ℃ and 3MPa H2Which catalyzes the HDO reaction of guaiacol under pressure. The main products detected are phenols, the yield of the phenol reaches 70%, experiments show that the low temperature is favorable for selectively generating phenol products, and compared with hydrocarbon solvents, the use of tetralin and decalin solvents is more favorable for reaction. However, it can be seen from the above experiments that for the Mo-based catalysts, the catalysts are all reduced, which consumes a large amount of H2It is not favorable for saving energy. In addition, the catalyst needs pre-reduction treatment, which not only complicates the preparation and maintenance process of the catalyst 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 compounded CoFe/rGO catalyst and a method for preparing phenol by catalytic hydrogenation of guaiacol.
The invention has the following inventive concept: the catalyst takes cheap transition metal Co as a hydrogenation active component, transition metal Fe as an auxiliary agent and reduced graphene oxide rGO as a carrier, and the prepared catalyst does not need high-temperature pre-reduction treatment and can be used for the reaction of preparing phenol by catalyzing and hydrogenating guaiacol. The synthesized catalyst does not need reduction pretreatment, generates higher catalytic activity and product selectivity under mild conditions, and provides a novel high-efficiency catalyst for preparing phenol by selective hydrogenation of guaiacol.
The purpose of the invention is realized by the following technical scheme:
a method for preparing phenol by catalytically hydrogenating guaiacol comprises the following steps: to rightDodecane is used as a solvent, and guaiacol reacts with H under the action of a CoFe/rGO catalyst2And reacting for 0.5-4h at 260-320 ℃ and 0.5-3 MPa to obtain phenol.
Further, the preparation of phenol by guaiacol hydrogenation adopts an intermittent kettle reaction, and comprises the following specific steps:
(1) loading a kettle: taking a mechanical stirring high-pressure reaction kettle, adding guaiacol, solvent n-dodecane, internal standard substance tetradecane and CoFe/rGO catalyst into the mechanical stirring high-pressure reaction kettle, screwing down the reaction kettle, checking the air tightness of the device, and introducing 1MPaH after ensuring that the device is airtight2；
(2) Reaction: setting the heating temperature of the reaction kettle to be 300 ℃, the reaction time to be 3h and the stirring speed to be 500 plus 800RPM, and starting the experiment;
(3) and (4) analyzing results: after the reaction is finished, collecting gas phase and liquid phase products, analyzing by using a gas chromatography, and recovering the catalyst by centrifuging;
the prepared CoFe/rGO catalyst does not need reduction pretreatment before being added into a reaction kettle.
Further, the usage amount 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 the hydrogenation catalytic function is Co, and the metal for assisting and adjusting the product selectivity 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) preparing a graphene carrier: 230mL of concentrated sulfuric acid and 5.0g of NaNO are taken3Adding 10g of natural flake graphite powder with stirring, adding 30g of KMnO after stirring for 2.5h4Transferring the mixture into a 35 ℃ constant temperature water bath for reaction for 2H, adding 460mL of deionized water, stirring the mixture in an oil bath at 98 ℃ for 15min, finally adding 1.4L of deionized water to stop the reaction, and simultaneously adding 25mL of 30% H2O2Cooling to room temperature, centrifugally washing with deionized water to neutrality, dispersing the prepared GO paste with dry content of 1g in 1000mL of deionized water, performing ultrasonic treatment for 30min, and standingAging, 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, carrying out suction filtration while hot, and carrying out freeze drying to obtain a rGO carrier for later use;
(2) preparation of salt solution: taking a certain amount of Co (NO)3)2·6H2O and Fe (NO)3)2·9H2Dissolving the mixture in a beaker by using deionized water and ethanol to prepare a salt solution;
(3) dipping: weighing corresponding amount of rGO, adding into the solution prepared in the step (2), continuously stirring 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 for drying for 12h at 50 ℃, and grinding the sample by using an agate mortar until the sample becomes powder;
(5) roasting: and (3) putting the powdery sample prepared in the step (4) into a quartz tube, putting the quartz tube into a tube furnace, raising the temperature from room temperature to 500 ℃ by a program of 10 ℃/min in the atmosphere of nitrogen, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, taking out the sample when the temperature is reduced to room temperature, and sealing and storing the sample.
Co (NO) in the step (2)3)2·6H2O and Fe (NO)3)2·9H2The mass ratio of O is 1: 0.2-1: 0.5, preferably 1: 0.35, and Co (NO)3)2·6H2The proportion relation of O and the carrier rGO is that each g of rGO supports 2.0mmol of Co.
Compared with the prior art, the invention has the following advantages and effects:
(1) the Fe auxiliary agent is introduced into the catalyst, so that the phenol selectivity is obviously improved. The activity of the pure Co catalytic component is too high, so that a benzene ring is easily saturated, the selectivity of the phenol aromatic compound is greatly reduced, and the cyclohexanol or cyclohexane by-product is finally obtained. Fe itself has very low hydrogenation activity for guaiacol. However, Fe is introduced into Co, and the Fe passivates the hydrogenation activity of Co to a certain extent, so that the reaction is stopped at the step of phenol.
(2) Graphene is introduced into the catalyst, and Fe plays an electronic regulation and control role on Co by virtue of the graphene. The graphene is a polycyclic aromatic molecule, the planar structure contains rich pi-electrons, and the graphene has good electric conduction characteristics, so that Co atoms and Fe atoms distributed on the crystal face of the graphene take the graphene as a bridge to generate an electronic synergistic effect, so that the phenol selectivity is improved, and the catalyst activity is improved
(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 is not inactivated 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 losing activity due to oxidation in the using process.
(4) The CoFe/rGO catalyst is prepared by adopting a dipping-roasting method, and the preparation method is simple and suitable for large-scale industrial preparation. Compared with Co/rGO catalyst, the CoFe/rGO catalyst selectively hydrogenolyzes carbon-oxygen bonds of carbonyl and hydroxyl under the regulation of Fe, obviously reduces the hydrogenation of carbon-carbon bonds of benzene rings, and has 1MPaH at 300 DEG C2And under the condition of 3h, the yield of the phenol can reach 66.6 percent, and the high selectivity to the phenol is reflected.
In conclusion, the CoFe/rGO catalyst has the characteristics of high reaction activity, high selectivity and the like when catalyzing the guaiacol hydrogenation reaction, the conversion rate of guaiacol in the reaction can reach 94%, the phenol selectivity can reach 70.8%, the catalyst does not need high-temperature pre-reduction in the reaction process, and the preparation method is suitable for industrial mass preparation and has obvious advantages and industrial application values.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be purchased from chemical companies.
The graphene is introduced into the catalyst, and not only plays a role of a carrier, but also can modulate the electronic characteristics of the metal active component, so that the excellent catalytic performance is generated. KUMAR Surender, KUMAR Divyaratan, KISHORE Brij, et al3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media[J]Applied Surface Science,2017,418:79-86, Co was studied using chronovoltammetry3Fe and Co3Fe-RGO catalyst, found graphene and Co3The strong electron synergy between Fe can protect Co3Fe is not oxidized and corroded. As a non-noble metal catalyst, Co3Fe-rGO has strong tolerance to alkali liquor when used in Oxygen Reduction Reaction (ORR). The graphene is a polycyclic large aromatic molecule, the planar structure contains rich pi-electrons, and the graphene has a good conductive characteristic, 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 invention is the innovation of combining Co, Fe and graphene to construct the catalyst. For guaiacol hydrogenation, one typical reaction route is that guaiacol is first hydrogenated to phenol, phenol is further hydrogenated to cyclohexanol, and cyclohexanol, if it is further hydrogenated, to cyclohexane. Firstly, the Fe auxiliary agent is introduced into the catalyst, so that the phenol selectivity is obviously improved. The pure Co catalytic component has too high activity, so that a benzene ring is easily saturated, the selectivity of the phenol aromatic compound is greatly reduced, and the cyclohexanol or cyclohexane by-product is finally obtained, which is detailed in comparative example 1. Fe itself has very low hydrogenation activity for guaiacol, as detailed in comparative example 2. However, the introduction of Fe into Co deactivates the hydrogenation activity of Co to some extent, and the reaction is stopped at the phenol step. And secondly, introducing graphene into the catalyst, wherein Fe plays an electronic regulation and control role on Co by virtue of the graphene. The graphene is a polycyclic aromatic molecule, the planar structure contains rich pi-electrons, and the graphene has good electric conduction property, so that Co and Fe atoms distributed on the crystal face of the graphene generate electron synergistic effect by taking the graphene as a bridge, thereby not only improving the selectivity of phenol, but also improving the activity of the catalyst. When HY zeolite molecular sieve is used as a carrier in the same method, the prepared CoFe/HY catalyst cannot show similar catalytic performance, and the details are shown in comparative example 3.
Examples 1-4 batch reactions at different reaction temperatures
1. Preparing a catalyst: a CoFe/rGO catalyst is prepared by adopting a dipping-roasting method, and the method comprises the following specific steps:
(1) preparing a graphene carrier: 230mL of concentrated sulfuric acid and 5.0g of NaNO are taken3Adding 10g of natural flake graphite powder with stirring, adding KMnO after stirring for 2.5h4Transferring the mixture into a 35 ℃ constant temperature water bath for reaction for 2H, adding 460mL of deionized water, stirring the mixture in an oil bath at 98 ℃ for 15min, finally adding 1.4L of deionized water to stop the reaction, and simultaneously adding 25mL of 30% H2O2Cooling to room temperature, centrifugally washing with deionized water, washing to neutrality, dispersing the prepared GO paste with a dry basis of 1g in 1000mL of deionized water, carrying out ultrasonic treatment for 30min, standing, 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, carrying out suction filtration while hot, and carrying out freeze drying to obtain the rGO carrier for later use.
(2) Preparation of salt solution: 58.2mg of Co (NO) was taken3)2·6H2O and 28.3mgFe (NO)3)2·9H2Dissolving O in 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 stirred continuously with a glass rod. Standing the sample at room temperature for 3 h;
(4) and (3) drying: placing the sample after standing in the step (3) in a vacuum drying oven for drying for 12h at 50 ℃, and grinding the sample by using an agate mortar until the sample becomes powder;
(5) roasting: putting the powdery sample prepared in the step (4) into a quartz tube, putting the quartz tube into a tube furnace, raising the temperature from room temperature to 500 ℃ by a program of 10 ℃/min in the atmosphere of nitrogen, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, taking out the sample when the temperature is reduced to the room temperature, and sealing and storing the sample;
2. reaction test: the performance of a CoFe/rGO catalyst for catalyzing the guaiacol hydrogenation reaction is tested by adopting an intermittent reaction, and the method comprises the following specific steps:
(1) taking a mechanical stirring high-pressure reaction kettle, adding 300.0mg of guaiacol, 10ml of n-dodecane, 120mg of tetradecane serving as an internal standard substance and 30mg of CoFe/rGO catalyst into the reaction kettle, and putting the reaction kettle into the reaction kettleScrewing down and checking the air tightness of the device, ensuring that the device is airtight, and then introducing 1MPaH2The stirring rate at 700rpm was set to the specified temperature for 3 h.
(2) After the reaction was completed, the liquid phase product was collected and analyzed by gas chromatography. The catalyst was recovered by centrifugation.
Wherein: the conversion of guaiacol was (amount of guaiacol substance at the start of reaction-amount of guaiacol substance at the end of reaction)/amount of guaiacol substance at the start of reaction × 100%
Yield of phenol is the amount of phenol substance at the end of the reaction/the amount of guaiacol substance at the start of the reaction × 100%
Phenol selectivity ═ yield of phenol/conversion of guaiacol × 100%
The chromatographic analysis conditions were: a 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 substance.
3. The reaction results are shown in Table 1
TABLE 1 results for different reaction temperatures
Examples 1-3 it can be seen that guaiacol is also converted at 260 c, but at a lower reaction rate; when the reaction temperature reaches 300 ℃, the guaiacol can achieve 94% of conversion rate and 66.6% of phenol yield; phenol selectivity decreases rapidly at 320 ℃, and phenol continues to be hydrogenated to cyclohexanol at elevated temperatures. The optimized reaction temperature is 300 ℃.
Examples 3 and 5 to 7 batch reactions at different reaction pressures
1. Preparing a catalyst: the same procedure was used to prepare the catalysts of examples 1-4.
2. Reaction test: the operation procedure was the same as that of the reaction test procedure in examples 1 to 4, and the specific reaction conditions were as follows: after ensuring the device is airtight, a specified pressure H is introduced2700rpm stirring rate, set temperature 300 ℃ for reaction for 3 h.
3. The reaction results are shown in Table 2.
TABLE 2 results of different reaction pressures
As seen in examples 3 and 5-7, the guaiacol conversion increased with increasing pressure when the reaction was carried out at 0.5MPa to 3MPa and 300 ℃ for 3 hours. When H is present2The catalyst has better catalytic activity when the pressure is 1.0MPa, and the yield of phenol can reach 66.6 percent; when the pressure was increased to 2.0MPa, the yield of phenol decreased. Continuously increase H2The pressure will cause further hydrogenation of the phenol to cyclohexanol. 1.0MPa of H2Is favorable for the reaction of catalyzing guaiacol to directionally generate phenol by the CoFe/rGO catalyst. The optimized hydrogen pressure is 1.0 MPa.
Examples 3 and 8-11 batch reactions with different reaction times
1. Preparing a catalyst: the same procedure was used to prepare the catalysts of examples 1-4.
2. Reaction test: the operation procedure was the same as that of the reaction test procedure in examples 1 to 4, and the specific reaction conditions were as follows: after ensuring the device is airtight, 1MPaH is introduced2700rpm stirring rate, set temperature 300 ℃ and reaction time specified.
3. The reaction results are shown in Table 3.
TABLE 3 results for different reaction times
Examples 3 and 8-11 it can be seen that H is at 300 ℃ and 1MPa2When the reaction time is 1h, the conversion rate of guaiacol is 74.9%, the yield of phenol is 46.7%, after the reaction time reaches 3h, the yield of phenol reaches 66.6%, and the reaction time is continuously prolonged, so that the yield of phenol begins to decrease. The phenol continues to react over time to produce cyclohexanol and cyclohexane. The optimized reaction time is 3 h.
Comparative example 1 batch reaction of Co/rGO catalyst
1. Preparing a catalyst: the method for preparing the Co/rGO catalyst by adopting a dipping-roasting method comprises the following specific steps:
(2) preparation of salt solution: 58.2mg of Co (NO)3)2·6H2O, preparing a salt solution by using 0.82mL of deionized water and 0.2mL of absolute ethyl alcohol;
the remaining preparation steps were as in examples 1 to 4.
2. Reaction test: the performance of the Co/rGO catalyst in catalyzing the guaiacol hydrogenation reaction is tested by adopting the batch reaction, and the specific steps are the same as those in examples 1-4.
The reaction result shows that the conversion rate of guaiacol is 100% and the selectivity of phenol is 0 under the action of the catalyst. Under the condition of the same proportion, the CoFe/rGO catalyst can control the reaction in the step of phenol, and the yield of phenol reaches 66.6%.
Comparative example 2 batch reaction of Fe/rGO catalyst
1. Preparing a catalyst: the preparation method of the Fe/rGO catalyst by adopting a dipping-roasting method comprises the following specific steps:
(2) preparation of salt solution: 28.3mg of Fe (NO)3)3·9H2O, preparing a salt solution by using 0.82mL of deionized water and 0.2mL of absolute ethyl alcohol;
the remaining preparation steps were as in examples 1 to 4.
2. Reaction test: the performance of the Fe/rGO catalyst in catalyzing the guaiacol hydrogenation reaction is tested by adopting an intermittent reaction, and the specific steps are the same as those in examples 1-4.
The reaction result shows that the conversion rate of guaiacol is about 2% under the action of the catalyst, and under the same proportion condition, the CoFe/rGO catalyst can completely convert guaiacol, and the yield of phenol reaches 66.6%.
In addition, the sum of the yield of phenol obtained by the reaction of the Co/rGO catalyst and the Fe/rGO catalyst is far lower than that of phenol obtained by the reaction of the CoFe/rGO catalyst, which shows that Co and Fe loaded on the surface of rGO are not simply physically superposed but form a synergistic effect to generate an excellent catalytic action.
Comparative example 3 batch reaction of CoFe/HY catalyst
1. Preparing a catalyst: the method for preparing the CoFe/HY catalyst by adopting a dipping-roasting method comprises the following specific steps:
(2) preparation of salt solution: 582mg of Co (NO) were taken3)2·6H2O and 283mg Fe (NO)3)2·9H2Dissolving O in 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, 1000mg of HY powder was weighed, added to the beaker, and continuously stirred with a glass rod. Standing the sample at room temperature for 3 h;
the remaining preparation steps were as in examples 1 to 4.
2. Reaction test: the performance of the CoFe/HY catalyst in catalyzing the guaiacol hydrogenation reaction is tested by adopting the batch reaction, and the specific steps are the same as those in examples 1-4.
The reaction result shows that guaiacol is not converted under the action of the catalyst. Under the condition of the same proportion, the CoFe/rGO catalyst disclosed by the invention can be used for completely converting guaiacol, and the yield of phenol reaches 66.6%.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (8)
1. A method for preparing phenol by catalytically hydrogenating guaiacol is characterized by comprising the following steps: taking n-dodecane as a solvent, and reacting guaiacol with H under the action of a CoFe/rGO catalyst2And reacting for 0.5-4h at 260-320 ℃ and 0.5-3 MPa to obtain phenol.
2. The method for preparing phenol by catalytically hydrogenating guaiacol as claimed in claim 1, wherein the step of preparing phenol by hydrogenating guaiacol by using a batch still reaction comprises the following steps:
(1) loading a kettle: adding guaiacol into a mechanically-stirred high-pressure reaction kettleSolvent n-dodecane, internal standard substance tetradecane and CoFe/rGO catalyst, screwing down a reaction kettle, checking the air tightness of the device, ensuring that 1MPaH is introduced after the device is airtight2；
(2) Reaction: setting the heating temperature of the reaction kettle to be 300 ℃, the reaction time to be 3h and the stirring speed to be 500 plus 800RPM, and starting the experiment;
(3) and (4) analyzing results: after the reaction, the gas and liquid phase products were collected and analyzed by gas chromatography, and the catalyst was recovered by centrifugation.
3. The method of claim 2, wherein the CoFe/rGO catalyst is prepared without a reduction pretreatment prior to being added to the reactor.
4. The method for preparing phenol by catalytically hydrogenating guaiacol as claimed in claim 1 or 2, wherein the amount of the CoFe/rGO catalyst is 10-80% by mass of guaiacol.
5. The method for preparing phenol by catalytically hydrogenating guaiacol as claimed in claim 1 or 2, wherein the CoFe/rGO catalyst is prepared by a dipping-roasting method, comprising the following steps:
(1) preparing a graphene carrier: 230mL of concentrated sulfuric acid and 5.0g of NaNO are taken3Adding 10g of natural flake graphite powder with stirring, adding 30g of KMnO after stirring for 2.5h4Transferring the mixture into a 35 ℃ constant temperature water bath for reaction for 2H, adding 460mL of deionized water, stirring the mixture in an oil bath at 98 ℃ for 15min, finally adding 1.4L of deionized water to stop the reaction, and simultaneously adding 25mL of 30% H2O2Cooling to room temperature, centrifugally washing with deionized water, washing to be neutral, dispersing the prepared GO paste with the dry basis content of 1g in 1000mL of deionized water, carrying out ultrasonic treatment for 30min, standing, 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, carrying out suction filtration while hot, and carrying out freeze drying to obtain an rGO carrier for later use;
(2) preparation of salt solution: taking a certain amountCo(NO3)2·6H2O and Fe (NO)3)2·9H2Dissolving the mixture in a beaker by using deionized water and ethanol to prepare a salt solution;
(3) dipping: weighing corresponding amount of rGO, adding into the solution prepared in the step (2), continuously stirring 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 for drying for 12h at 50 ℃, and grinding the sample by using an agate mortar until the sample becomes powder;
(5) roasting: and (3) putting the powdery sample prepared in the step (4) into a quartz tube, putting the quartz tube into a tube furnace, raising the temperature from room temperature to 500 ℃ by a program of 10 ℃/min in the atmosphere of nitrogen, roasting the quartz tube at the constant temperature of 500 ℃ for 2 hours, taking out the sample when the temperature is reduced to room temperature, and sealing and storing the sample.
6. The process for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 5, wherein Co (NO) in the step (2)3)2·6H2O and Fe (NO)3)2·9H2The mass ratio of O is 1: 0.2-1: 0.5.
7. The process for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 5, wherein Co (NO) in the step (2)3)2·6H2O and Fe (NO)3)2·9H2The mass ratio of O is 1: 0.35.
8. the process for preparing phenol by catalytic hydrogenation of guaiacol as claimed in claim 5, wherein Co (NO) in the step (2)3)2·6H2The proportion relationship of O and the carrier rGO is that each g of rGO carries 2.0mmol of Co.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210099380.3A CN114478198B (en) | 2022-01-27 | 2022-01-27 | Method for preparing phenol by catalytic hydrogenation of guaiacol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210099380.3A CN114478198B (en) | 2022-01-27 | 2022-01-27 | Method for preparing phenol by catalytic hydrogenation of guaiacol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114478198A true CN114478198A (en) | 2022-05-13 |
| CN114478198B CN114478198B (en) | 2023-07-21 |
Family
ID=81477222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210099380.3A Active CN114478198B (en) | 2022-01-27 | 2022-01-27 | Method for preparing phenol by catalytic hydrogenation of guaiacol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114478198B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE741686C (en) * | 1939-07-30 | 1943-11-18 | Revisions Und Treuhand Ag Deut | Process for the production of phenols, their offsets and hydrogenated phenols by pressure hydrogenation of lignin or lignin-containing substances |
| US20010049330A1 (en) * | 1997-07-05 | 2001-12-06 | Kustov Leonid Modestovich | Preparation of catalysts useful in the preparation of phenol and its derivatives |
| KR20130011296A (en) * | 2011-07-21 | 2013-01-30 | 고려대학교 산학협력단 | The method of aromatic compounds production using tungsten oxide alumina catalyst for hydrodeoxygenation of guaiacol |
| US20160289150A1 (en) * | 2013-10-27 | 2016-10-06 | Purdue Research Foundation | Catalytic biomass conversion methods, catalysts, and methods of making the same |
| CN106423233A (en) * | 2016-09-12 | 2017-02-22 | 天津大学 | Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction |
| CN106554257A (en) * | 2015-09-30 | 2017-04-05 | 中国科学院大连化学物理研究所 | The method that phenol and aldehydes matter are prepared by guaiacol or alkyl guaiacol |
| US20190144590A1 (en) * | 2015-07-13 | 2019-05-16 | University Of Delaware | Bio-based polymers from raw lignocellulosic biomass |
| CN110152672A (en) * | 2019-04-08 | 2019-08-23 | 浙江师范大学 | A kind of nickel-base catalyst prepares the purposes of the catalyst of phenol and cyclohexanol as guaiacol |
| CN112778083A (en) * | 2020-12-31 | 2021-05-11 | 大连大学 | Method for synthesizing cyclohexanol by using 2, 6-dimethoxyphenol |
| CN113731441A (en) * | 2021-09-28 | 2021-12-03 | 大连大学 | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof |
-
2022
- 2022-01-27 CN CN202210099380.3A patent/CN114478198B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE741686C (en) * | 1939-07-30 | 1943-11-18 | Revisions Und Treuhand Ag Deut | Process for the production of phenols, their offsets and hydrogenated phenols by pressure hydrogenation of lignin or lignin-containing substances |
| US20010049330A1 (en) * | 1997-07-05 | 2001-12-06 | Kustov Leonid Modestovich | Preparation of catalysts useful in the preparation of phenol and its derivatives |
| KR20130011296A (en) * | 2011-07-21 | 2013-01-30 | 고려대학교 산학협력단 | The method of aromatic compounds production using tungsten oxide alumina catalyst for hydrodeoxygenation of guaiacol |
| US20160289150A1 (en) * | 2013-10-27 | 2016-10-06 | Purdue Research Foundation | Catalytic biomass conversion methods, catalysts, and methods of making the same |
| US20190144590A1 (en) * | 2015-07-13 | 2019-05-16 | University Of Delaware | Bio-based polymers from raw lignocellulosic biomass |
| CN106554257A (en) * | 2015-09-30 | 2017-04-05 | 中国科学院大连化学物理研究所 | The method that phenol and aldehydes matter are prepared by guaiacol or alkyl guaiacol |
| CN106423233A (en) * | 2016-09-12 | 2017-02-22 | 天津大学 | Transition metal phosphide catalyst, preparing method and application to guaiacol hydrogenolysis reaction |
| CN110152672A (en) * | 2019-04-08 | 2019-08-23 | 浙江师范大学 | A kind of nickel-base catalyst prepares the purposes of the catalyst of phenol and cyclohexanol as guaiacol |
| CN112778083A (en) * | 2020-12-31 | 2021-05-11 | 大连大学 | Method for synthesizing cyclohexanol by using 2, 6-dimethoxyphenol |
| CN113731441A (en) * | 2021-09-28 | 2021-12-03 | 大连大学 | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ASSUSCEPTORSB. DEBALINA ET AL.: "Production of carbon nanostructures in biochar, bio-oil and gasesfrom bagasse via microwave assisted pyrolysis using Fe and Co assusceptors", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》, vol. 124, pages 310 * |
| 吕洋: "石墨烯材料在催化剂中应用功能综述", 《工业催化》, vol. 29, no. 5, pages 1 - 9 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114478198B (en) | 2023-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108048125B (en) | Method for preparing aromatic hydrocarbon by high-selectivity catalytic transfer hydrogenation of lignin derivatives | |
| CN113101933A (en) | Supported nickel-cobalt bimetallic nano catalyst and application thereof in catalyzing selective hydrogenation reaction of vanillin | |
| CN109384750B (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN111875566A (en) | Method for preparing 2, 5-dimethylfuran | |
| CN109794245A (en) | A kind of iron-based hydrogenation catalyst (Fe of honeycomb3O4@C)/C and its preparation method and application | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN105854908A (en) | Photocatalyst for preparation of hydrogen and corresponding aldehyde and ketone by means of alcohol decomposition | |
| CN105837391B (en) | A kind of application of no catalytic hydrogenation in catalytic benzene hydrogenation reaction | |
| CN108623436B (en) | Method for converting cellulose into bioethanol by one-pot method | |
| CN112138698A (en) | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction | |
| CN108409692A (en) | A kind of method that the carbon material supported ruthenium catalyst catalysis levulic acid Hydrogenation of sulfur doping takes gamma-valerolactone | |
| CN112778243B (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN111087370A (en) | Method for preparing furfuryl alcohol by catalyzing furfural transfer hydrogenation through nitrogen-doped carbon loaded by non-noble metal | |
| CN108383677A (en) | A method of catalysis australene Hydrogenation is for cis-pinane | |
| CN115138392B (en) | Multifunctional biochar catalyst rich in oxygen-containing functional groups and preparation method thereof | |
| CN114478198B (en) | Method for preparing phenol by catalytic hydrogenation of guaiacol | |
| CN109535108A (en) | A kind of preparation method of 2,5- dimethyl furan | |
| CN114308132B (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| KR20130017250A (en) | Method for preparing high-yield biofuel from guaiacol | |
| CN111715252B (en) | Method for catalytically synthesizing organic compound, catalyst and application thereof | |
| CN111203224B (en) | Method for preparing green catalyst by using biomass tar and application | |
| CN113292519A (en) | Magnetic gold-cobalt composite catalyst and preparation method and application thereof | |
| CN111389395A (en) | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural | |
| CN108636434B (en) | Composite photocatalyst for photocatalytic water decomposition and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |