CN113336626B - Phenol selective hydrogenation method on B modified NiCo catalyst - Google Patents

Phenol selective hydrogenation method on B modified NiCo catalyst Download PDF

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CN113336626B
CN113336626B CN202110666579.5A CN202110666579A CN113336626B CN 113336626 B CN113336626 B CN 113336626B CN 202110666579 A CN202110666579 A CN 202110666579A CN 113336626 B CN113336626 B CN 113336626B
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nicob
phenol
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CN113336626A (en
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陈彦广
蒋博龙
王欢
李锋
张梅
王园园
张春雷
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Northeast Petroleum University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • 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
    • B01J23/755—Nickel
    • 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
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    • 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
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a phenol selective hydrogenation method on a B modified NiCo catalyst, which comprises the following steps: (1) Taking NiCoB-MOF-74 as a precursor, soaking in an alcohol solution, and regulating and controlling through a pyrolysis process to obtain a carbon-coated nano-scale catalyst precursor NiCoB@C; (2) Soaking NiCoB@C in alcohol solution, and then soaking in NH 3 Treating under atmosphere to obtain a high-activity surface-modified NiCoB@C-Surf catalyst; (3) Establishing a catalytic reaction system taking a mixed hydrogen-supplying solvent system as a solvent; (4) Based on the steps (1), (2) and (3), the activity of the catalyst is improved, the adsorption effect of phenol on the surface of the catalyst is enhanced, the selective hydrogenation speed of phenol on the NiCoB@C-Surf catalyst is accelerated, and the reaction is carried out for 1.5-2 hours, so that the phenol is completely converted into cyclohexanol. The invention has low cost, fast reaction rate and short reaction time.

Description

Phenol selective hydrogenation method on B modified NiCo catalyst
Technical field:
the invention belongs to the technical field of catalysis, and particularly relates to a phenol selective hydrogenation method on a B modified NiCo catalyst.
The background technology is as follows:
cyclohexanol is an important raw material in the polymerization industry and is also one of the raw materials for the production of nylon and plasticizers. Cyclohexanol can also be used for manufacturing plasticizers, surfactants, detergents, emulsion stabilizers and the like, and has wide application fields. At present, the production process of cyclohexanol mainly comprises a cyclohexane oxidation method and a phenol hydrogenation method. Among them, the cyclohexane oxidation method has the advantages of relatively low cost, severe reaction conditions, low yield and complex separation steps. Compared with cyclohexane oxidation, the phenol hydrogenation method has the advantages of high operation safety, low energy consumption, short process flow, less side reaction, easy separation of products and the like, and has wider application value.
The noble metal catalyst has good phenol hydrogenation catalytic activity, but noble metal is rare and expensive, so that the large-scale application of the noble metal catalyst is limited. Therefore, transition metal catalysts (Ni, co, fe, etc.) having a price advantage are receiving general attention in the reaction of hydrogenating phenol to make cyclohexanol. However, the existing transition metal catalyst has low phenol hydrogenation activity, the product is often a mixture of cyclohexanol and cyclohexanone, and the selectivity is not ideal. Therefore, the design of the high-performance efficient transition metal catalyst with the cyclohexanol selectivity of 100% by phenol hydrogenation has important significance.
Literature [ Aiqin Li: highly selective hydrogenation of phenol to cyclohexanol over MOF-determined non-noble Co-Ni@NC catalysts, doi: http:// dx.doi.org/10.1016/j.cs.2017.03.027]MOF materials were synthesized using transition metal Ni and Co nitrates, terephthalic acid organic ligands and triethyldiamine in N, N-dimethylformamide solvent, via 600 o Ni@NC-600 and Co@NC-600 catalysts were prepared by C pyrolysis. Under 100 ℃ and 0.8MPa, isopropanol is used as solvent to react for 12 hours, the phenol conversion rates of Ni@NC-600 and Co@NC-600 catalysts are 23.2% and 35.2%, respectively, and the cyclohexanol selectivity is high>99.9%. However, the single metal catalyst has a problem of too low phenol conversion because the reaction time is long (12 hours). And then they prepared bimetallic NiCo@NC-600 catalyst, and reacted for 12 hours at 100 ℃ and 0.8MPa with isopropanol as solvent, the conversion rate and cyclohexanol selectivity were both greater than 99.9%, but the reaction time was still very long (12 hours). Chinese patent application with publication number of CN104447209A, which is prepared by reacting glucosamine salt and melamine with cobalt or nickel salt to obtain porous carbon material supported Co and Ni catalyst for preparing cyclohexanol by phenol hydrogenation, and reacting at 3MPa and reaction temperature of 150 o C, the conversion rate reaches 100%, and the cyclohexanol selectivity is over 99%, but the reaction time is too long (12-30 hours), and the reaction rate is slow. Therefore, the transition metal with low cost is developed as active groupThe catalyst for preparing cyclohexanol from phenol has the advantages of short reaction time, high selectivity and good activity, and has important practical significance.
In addition to the activity of the catalyst during heterogeneous catalytic reactions, the mass transfer rate of the reaction feed is another critical factor affecting the catalytic reaction. The activity of the catalyst is high, but the reactant phenol can not reach an active site in time, so that the whole reaction rate is seriously influenced, and the reaction time is long; on the contrary, the catalytic activity is low, the mass transfer effect is good again, and high conversion rate and selectivity cannot be achieved. The invention provides a preparation method of a C-coated high-activity NiCoB@C-Surf catalyst by taking NiCoB-MOF-74 as a precursor, wherein in a catalytic reaction system taking a mixed hydrogen supply solvent system as a solvent, the hydrogenation catalytic activity and selectivity are improved by selecting and preparing a catalyst precursor, preparing a route, preparing conditions and designing the catalytic reaction system, (1) regulating and controlling the size, dispersity, surface property and hydrogen supply capacity of the reaction system of metal nano particles; (2) The dissolubility of the solvent system to phenol and the adsorption performance of the catalyst to phenol are regulated and controlled, and the time for the phenol raw material to reach the active center of the catalyst is shortened. Through perfect combination of catalytic activity and phenol mass transfer, an excellent phenol hydrogenation catalytic effect is realized.
The invention comprises the following steps:
the invention aims to provide a phenol selective hydrogenation method on a B modified NiCo catalyst, and a catalytic reaction system thereof, and provides a method for preparing cyclohexanol by high-efficiency hydrogenation of phenol, which is used for solving the problems of low conversion rate and long reaction time of the catalyst for preparing cyclohexanol by phenol hydrogenation in the prior art.
The technical scheme adopted for solving the technical problems is as follows: the phenol selective hydrogenation method on the B modified NiCo catalyst comprises the following steps:
(1) Taking NiCoB-MOF-74 as a precursor, soaking the precursor in an alcohol solution, and regulating and controlling the precursor through a pyrolysis process under inert atmosphere and pyrolysis temperature to obtain a carbon-coated nano-scale catalyst precursor NiCoB@C;
(2) Soaking NiCoB@C in alcohol solution, and then soaking in NH 3 Treating under atmosphere to obtain high-activity surface-modified NiCoB@C-SA url catalyst;
(3) Establishing a catalytic reaction system taking a mixed hydrogen-supplying solvent system as a solvent;
(4) Under certain hydrogen partial pressure and reaction temperature, the activity of the catalyst is improved based on (1), (2) and (3), the adsorption effect of phenol on the surface of the catalyst is enhanced, the selective hydrogenation speed of phenol on the NiCoB@C-Surf catalyst is accelerated, the hydrogen partial pressure is 2-3 MPa at the reaction temperature of 80-120 ℃, the reaction time is 1.5-2 hours, the phenol is completely converted into cyclohexanol, and the catalyst can be recycled after separation.
In the NiCoB-MOF-74 precursor, the molar ratio of nickel salt to cobalt salt is 1:1.2-4, the ratio of the molar amount of B to the total molar amount of the two metal salts is 1-2:5, and the added B is boric acid.
The soaking treatment in the alcohol solution in the scheme refers to soaking the NiCoB-MOF-74 precursor in the alcohol solution for 8-24 hours, removing surface residues, filtering, alternately washing with alcohol and water for 3-6 times, and vacuum drying for 8-24 hours at 50-120 ℃.
When preparing a catalyst precursor NiCoB@C under inert atmosphere by regulating and controlling pyrolysis conditions in the scheme: and pyrolyzing the NiCoB-MOF-74 precursor in an argon atmosphere at a heating rate of 3-5 ℃/min, a pyrolysis temperature of 500-600 ℃ and a pyrolysis time of 2-3 hours to obtain a catalyst precursor NiCoB@C.
The step of soaking the NiCoB@C in the alcohol solution is to soak the NiCoB@C in the alcohol solution for 8-24 hours, remove surface residues, perform suction filtration, alternately wash the NiCoB@C with ethanol and water for 3-6 times, and perform vacuum drying at 50-120 ℃ for 8-24 hours.
In NH as described in the above scheme 3 Treatment under atmosphere means treatment under NH 3 And (3) under the atmosphere, the temperature rising rate is 3-5 ℃/min, the temperature is 350-380 ℃, and the treatment is carried out for 30-60 minutes, so that the NiCoB@C-Surf catalyst is obtained.
The hydrogen supply solvent system in the scheme is a mixed solvent of isopropanol and one of decalin, tetrahydronaphthalene and dihydronaphthalene, wherein the mass fraction of the isopropanol is 20-40%.
The mass fraction of the phenol in the hydrogen-supplying solvent reaction system is 2-5%.
The addition amount of the NiCoB@C-Surf catalyst in the scheme is that the mass ratio of the NiCoB@C-Surf catalyst to the phenol solution is 0.0005-0.002:1.
The catalyst separation method in the scheme adopts magnetic separation, and the activity and the selectivity of the separated catalyst are unchanged after the catalyst is circularly used for 5 times through reaction separation.
The invention has the following beneficial effects:
(1) The catalyst of the invention adopts non-noble metal Ni and Co bimetallic as active components, and has the characteristics of low cost, fast reaction rate, short reaction time, high activity, good selectivity and the like.
(2) The method for preparing cyclohexanol by phenol selective hydrogenation has the characteristics of high phenol hydrogenation activity and high cyclohexanol selectivity, and is characterized in that measures are taken from three aspects of a catalyst preparation route, a preparation method and a reaction system: (a) On a catalyst preparation route, a metal organic framework NiCoB-MOF-74 is selected as a catalyst precursor, and metal nano particles are limited in a narrow range by means of strong coordination action between metal and organic ligand and domain limiting action of MOF, so that aggregation and growth of the particles are prevented, and more metal active sites are exposed; (b) In the preparation method of the catalyst, the doping of hetero atom B into the carbon substrate of the catalyst is realized through boric acid modification, so that the positive charge density of adjacent carbon atoms is increased, and uneven charge is induced, thereby improving the H of metal 2 Activating the cleavage capacity; the metal Ni and Co in the catalyst have isolation effect, so that agglomeration of metal particles can be further inhibited; electrons are transferred from metal Ni to Co, and the synergistic effect between Ni and Co ensures that the bimetal has higher activity; pretreatment is adopted for NiCoB-MOF-74, impurities are removed, and the activity of the catalyst is improved; the catalyst is subjected to surface modification through alcohol and ammonia treatment, and the electron distribution and the surface property on the surface of the catalyst are changed, so that the phenol hydrogenation activity and the cyclohexanol selectivity are improved; (c) The invention adopts the mixed system of isopropanol and one of decalin, tetrahydronaphthalene and dihydronaphthalene as the reaction systemThe catalytic reaction system of the solvent has excellent hydrogen storage performance and good hydrogen transfer function, can rapidly provide hydrogen required by phenol hydrogenation reaction, and improves the phenol hydrogenation activity and cyclohexanol selectivity of the catalyst.
(3) The method for preparing cyclohexanol by phenol selective hydrogenation has the characteristics of high phenol hydrogenation reaction speed and short reaction time, and the catalyst and the catalytic reaction system constructed by the method accelerate the time for the reactant phenol to reach the active site of the catalyst: (a) The NiCoB-MOF-74 precursor used in the invention is prepared by taking 2, 5-dihydroxyterephthalic acid as an organic ligand, so that the surface of the prepared NiCoB@C-Surf catalyst contains an-OH group which can react with the-OH group in phenol through hydrogen bond to promote the adsorption of reactant phenol on the surface of the catalyst and accelerate the time required for the reactant to reach the active site of the catalyst; (b) B in the catalyst carbon substrate reacts with hydroxyl in the phenol to form B.H-O, so that the adsorption capacity of the catalyst on the phenol is improved, and the phenol can quickly reach the surface of the catalyst. (c) The invention provides a catalytic reaction system which takes a mixed system of decalin, tetrahydronaphthalene and dihydronaphthalene and isopropanol as a solvent, and the solvent has good solubility to phenol and can promote the sufficient contact between the phenol and a catalyst; (d) The surface of the catalyst is modified through alcohol treatment and ammonia treatment, so that the surface property of the catalyst is changed, and the adsorption of reactant phenol on the active site of the catalyst is accelerated.
(4) The method for preparing cyclohexanol by phenol selective hydrogenation provided by the invention can reach 100% of phenol conversion rate within 2 hours, and the cyclohexanol selectivity is 100%. Compared with the prior art (12 hours), the method has the characteristic of short reaction time on the premise that the phenol conversion rate and the cyclohexanol selectivity are 100 percent. This is mainly due to the fact that the nicob@c-Surf catalyst of the present invention has high activity, and by enhancing the adsorption of phenol on the catalyst surface, the phenol required for the reaction is rapidly supplied to the active sites on the catalyst surface. The method has the advantages of high hydrogenation activity of phenol, good selectivity of cyclohexanol, short reaction time, high activity and rapid mass transfer. Therefore, the invention realizes perfect combination of activity and mass transfer, thereby achieving excellent reaction results.
(5) In the catalyst provided by the invention, as the active phase is the carbon-coated NiCo bimetallic nano particles, the active component is protected by the carbon layer, and the catalyst has magnetism and can be separated from a reaction product by using a magnet. Therefore, the catalyst surface has excellent stability, convenient recovery and good reusability.
Description of the drawings:
FIG. 1 is a schematic diagram of the synthetic route to a NiCoB@C-Surf catalyst.
FIG. 2 is an XRD pattern for a NiCoB@C-Surf catalyst.
FIG. 3 is a TEM image of a NiCoB@C-Surf catalyst.
FIG. 4 is a graph of NiCoB@C-Surf catalyst activity and selectivity as a function of time.
FIG. 5 is a schematic diagram of NiCoB@C-Surf catalyst recovery.
FIG. 6 is a graph of the reusability of NiCoB@C-Surf catalyst.
The specific embodiment is as follows:
the invention is further described below with reference to the accompanying drawings:
example 1:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
the synthetic route of the NiCoB@C-Surf catalyst is shown in fig. 1, and a catalyst precursor NiCoB@C is synthesized firstly, specifically as follows:
the NiCoB-MOF-74 is soaked in ethanol solution for 8 hours at room temperature, surface residues are removed, suction filtration and alternate washing with ethanol and water are carried out for 6 times, and vacuum drying is carried out for 18 hours at 60 ℃ to obtain the pure NiCoB-MOF-74. The pure NiCoB-MOF-74 is placed in a tube furnace, pyrolyzed in argon atmosphere, the temperature is raised to 550 ℃ from room temperature at the heating rate of 3 ℃/min, the temperature is kept for 2 hours, and the temperature is reduced to the room temperature, so as to obtain a catalyst precursor NiCoB@C of the carbon-coated nano-scale metal.
Wherein the preparation of NiCoB-MOF-74:
adding nickel acetate and cobalt acetate into distilled water to prepare a solution with the total concentration of metal salt of 0.20mol/L, wherein the molar ratio of the nickel acetate to the cobalt acetate is 1:1.2; 2, 5-dihydroxyterephthalic acid was added to the solvent in tetrahydrofuran to prepare an organic ligand solution having a 2, 5-dihydroxyterephthalic acid concentration of 0.08 mol/L. Respectively stirring the two solutions for 10 minutes, mixing, adding boric acid, and stirring for 30 minutes, wherein the ratio of the molar quantity of the organic ligand to the total molar quantity of the two metal salts is 1:4, and the ratio of the molar quantity of the boric acid to the total molar quantity of the two metal salts is 1:5; transferring the mixed solution to a polytetrafluoroethylene reaction kettle, putting the mixed solution into an oven, performing hydrothermal reaction for 60 hours at 100 ℃, cooling, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 120 ℃ for 6 hours to obtain NiCoB-MOF-74.
2) Preparation of NiCoB@C-Surf catalyst:
as shown in FIG. 1, niCoB@C obtained in 1) above was immersed in an ethanol solution for 8 hours, the surface residue was removed, suction-filtered, washed alternately with ethanol and water 6 times, and dried under vacuum at 60℃for 18 hours. Placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 And (3) processing under atmosphere, wherein the temperature is increased to 380 ℃ from room temperature at a heating rate of 3 ℃/min, the temperature is kept for 60 minutes, and the temperature is reduced to room temperature, so that the NiCoB@C-Surf catalyst is obtained.
XRD characterization of NiCoB@C-Surf catalyst:
XRD characterization was performed on the NiCoB@C-Surf catalyst obtained in the step 2), and the active phase in the tested catalyst was analyzed, so that the result shows that characteristic peaks of metal Ni and Co alloy appear at 44.3 degrees, 51.7 degrees and 76.7 degrees (see figure 2), and the active phase in the NiCoB@C-Surf catalyst exists in the form of NiCo alloy. Diffraction peaks of other phases are not seen in the spectrogram, which shows that only single metal alloy nano particles are arranged in the catalyst, and other impurity phases are not generated.
Example 2:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
the NiCoB-MOF-74 is soaked in ethanol solution for 24 hours at room temperature, surface residues are removed, suction filtration and alternate washing with ethanol and water are carried out for 4 times, and vacuum drying is carried out for 8 hours at 120 ℃ to obtain the pure NiCoB-MOF-74. The pure NiCoB-MOF-74 is placed in a tube furnace, pyrolyzed in argon atmosphere, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, the temperature is kept for 3 hours, and the temperature is reduced to the room temperature, so as to obtain a catalyst precursor NiCoB@C of the carbon-coated nano-scale metal.
Wherein the preparation of NiCoB-MOF-74:
adding nickel acetate and cobalt acetate into distilled water to prepare a solution with the total concentration of metal salt of 0.10 mol/L, wherein the molar ratio of the nickel acetate to the cobalt acetate is 1:4; 2, 5-dihydroxyterephthalic acid was added to the solvent in tetrahydrofuran to prepare an organic ligand solution having a 2, 5-dihydroxyterephthalic acid concentration of 0.05 mol/L. Respectively stirring the two solutions for 10 minutes, mixing, adding boric acid, and stirring for 30 minutes, wherein the ratio of the molar quantity of the organic ligand to the total molar quantity of the two metal salts is 1:8, and the ratio of the molar quantity of the boric acid to the total molar quantity of the two metal salts is 2:5; transferring the mixed solution to a polytetrafluoroethylene reaction kettle, putting the mixed solution into an oven, performing hydrothermal reaction for 45 hours at 120 ℃, cooling, performing suction filtration, alternately washing with ethanol and water for 3 times, and performing vacuum drying at 80 ℃ for 12 hours to obtain NiCoB-MOF-74.
2) Preparation of NiCoB@C-Surf catalyst:
the resulting nicob@c was removed from the surface residue in ethanol solution for 24 hours, suction filtered, washed alternately with ethanol and water 6 times and dried under vacuum at 60 ℃ for 18 hours. Placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 And (3) processing under atmosphere, wherein the temperature is increased to 350 ℃ from room temperature at a heating rate of 5 ℃/min, the temperature is kept for 50 minutes, and the temperature is reduced to the room temperature, so that the NiCoB@C-Surf catalyst is obtained.
Characterization of NiCoB@C-Surf catalyst TEM:
TEM characterization is carried out on the NiCoB@C-Surf catalyst obtained in the step 2), the size of an active phase in the test catalyst is analyzed, the result is shown in fig. 3, the metal nano particles are uniformly distributed and have no obvious aggregation, and the nano particles are clearly seen to be coated by carbon from a large magnification image. In the catalyst, the average particle diameter of the metal nano particles is only about 3.0-5.0 nm. The small size and uniform dispersion of the metal nano particles are one of the keys that the catalyst has high phenol conversion rate and can be converted into cyclohexanol in a short time.
Example 3:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
the NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:1.5 and the ratio of boric acid molar amount to total molar amount of two metal salts of 1.5:5 is soaked in ethanol solution for 16 hours at room temperature, surface residues are removed, suction filtration and alternate washing with ethanol and water are carried out for 3 times, and vacuum drying is carried out at 120 ℃ for 8 hours, thus obtaining the pure NiCoB-MOF-74. The pure NiCoB-MOF-74 is placed in a tube furnace, pyrolyzed in argon atmosphere, the temperature is raised to 550 ℃ from room temperature at the heating rate of 3 ℃/min, the temperature is kept for 3 hours, and the temperature is reduced to the room temperature, so as to obtain a catalyst precursor NiCoB@C of the carbon-coated nano-scale metal.
2) Preparation of NiCoB@C-Surf catalyst:
soaking the obtained NiCoB@C in an ethanol solution for 16 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 60 ℃ for 18 hours; placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 And (3) processing under atmosphere, wherein the temperature is increased to 360 ℃ from room temperature at a heating rate of 5 ℃/min, the temperature is kept for 40 minutes, and the temperature is reduced to the room temperature, so that the NiCoB@C-Surf catalyst is obtained.
The NiCoB@C-Surf catalyst obtained in the embodiment is used for phenol hydrogenation reaction:
NiCoB@C-Surf catalyst is used for preparing cyclohexanol by phenol selective hydrogenation. The method comprises the steps of taking a mixture of tetrahydronaphthalene and isopropanol as a solvent, wherein the mass fraction of the isopropanol is 20%, and preparing a reaction solution system with the mass fraction of phenol being 5%. Adding a NiCoB@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, sealing the reaction kettle, detecting the leakage of nitrogen, replacing with hydrogen for three times, introducing hydrogen, stirring at 80 ℃ and 3MPa for reacting for 2 hours, and stopping the reaction; cooling the reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst from the product by using a magnet, and taking supernatant liquid to analyze the product composition by using gas chromatography. As a result of the experiment, the conversion of phenol was 100%, and the selectivity of cyclohexanol was 100%.
Example 4:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
and (3) soaking the NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:2 and the ratio of boric acid molar amount to total molar amount of two metal salts of 1.7:5 in ethanol solution for 12 hours at room temperature, removing surface residues, carrying out suction filtration, alternately washing with ethanol and water for 3 times, and carrying out vacuum drying at 120 ℃ for 8 hours to obtain the pure NiCoB-MOF-74. The pure NiCoB-MOF-74 is placed in a tube furnace, pyrolyzed in argon atmosphere, the temperature is raised to 550 ℃ from room temperature at the heating rate of 3 ℃/min, the temperature is kept for 3 hours, and the temperature is reduced to the room temperature, so as to obtain a catalyst precursor NiCoB@C of the carbon-coated nano-scale metal.
2) Preparation of NiCoB@C-Surf catalyst:
soaking the obtained NiCoB@C in an ethanol solution for 24 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 60 ℃ for 18 hours; placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 And (3) processing under atmosphere, wherein the temperature is increased to 350 ℃ from room temperature at a heating rate of 3 ℃/min, the temperature is kept for 60 minutes, and the temperature is reduced to the room temperature, so that the NiCoB@C-Surf catalyst is obtained.
The NiCoB@C-Surf catalyst obtained in the embodiment is used for phenol hydrogenation reaction:
NiCoB@C-Surf catalyst is used for preparing cyclohexanol by phenol selective hydrogenation. The method comprises the steps of taking a mixture of dihydronaphthalene and isopropanol as a solvent, wherein the mass fraction of the isopropanol is 40%, and preparing a reaction solution system with the mass fraction of phenol being 2%. Adding a NiCoB@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.0005:1, sealing the reaction kettle, detecting the leakage of nitrogen, replacing with hydrogen for three times, introducing hydrogen, stirring at 100 ℃ and 3MPa for reacting for 1.5 hours, and stopping the reaction; cooling the reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst from the product by using a magnet, and taking supernatant liquid to analyze the product composition by using gas chromatography. As a result of the experiment, the conversion of phenol was 100%, and the selectivity of cyclohexanol was 100%.
Example 5:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
and (3) soaking the NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:3 and the ratio of boric acid molar amount to total molar amount of two metal salts of 1.5:5 in ethanol solution for 20 hours at room temperature, removing surface residues, carrying out suction filtration, alternately washing with ethanol and water for 6 times, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain the pure NiCoB-MOF-74. And (3) placing the obtained pure NiCoB-MOF-74 in a tubular furnace, carrying out pyrolysis in an argon atmosphere, raising the temperature from room temperature to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, and cooling to the room temperature to obtain a carbon-coated nano-scale metal catalyst precursor NiCoB@C.
2) Preparation of NiCoB@C-Surf catalyst:
the obtained NiCoB@C was immersed in an ethanol solution for 20 hours, the surface residues were removed, suction-filtered, washed alternately with ethanol and water 6 times, and dried under vacuum at 80℃for 12 hours. Placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 Surface treatment is carried out under atmosphere, the temperature is increased to 380 ℃ from room temperature at a heating rate of 3 ℃/min, the temperature is kept for 40 min, and the temperature is reduced to room temperature, so that the NiCoB@C-Surf catalyst is obtained.
The effect of adding boric acid on the hydrogenation performance of the phenol catalyst was investigated by this example:
to investigate the effect of boric acid, the operations of steps 1) and 2) were performed exactly to give a NiCo@C-Surf catalyst, except that a molar ratio of nickel to cobalt of 1:3 NiCoB-MOF-74 was used in step 1).
Under the same reaction conditions, the NiCo@C-Surf catalyst and the NiCoB@C-Surf prepared in the example are respectively used for experiments of preparing cyclohexanol by phenol selective hydrogenation:
experiment 1: the method comprises the steps of taking a mixture of decalin and isopropanol as a solvent, wherein the mass fraction of isopropanol is 30%, and preparing a reaction solution system with the mass fraction of phenol being 3%. Adding a NiCoB@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leak of nitrogen, replacing with hydrogen for three times, introducing hydrogen, stirring at 120 ℃ and 2MPa for reacting for 1.0 hour, and stopping the reaction; cooling the high-pressure reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst from the product by using a magnet, and taking supernatant liquid to analyze the product composition by using gas chromatography. As a result of the experiment, the conversion of phenol of the NiCoB@C-Surf catalyst was 84.6%, and the cyclohexanol selectivity was 100%.
Experiment 2: the method comprises the steps of taking a mixture of decalin and isopropanol as a solvent, wherein the mass fraction of isopropanol is 30%, and preparing a reaction solution system with the mass fraction of phenol being 3%. Adding a NiCo@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leakage of nitrogen, replacing with hydrogen for three times, introducing hydrogen, stirring at 120 ℃ and 2MPa for reacting for 1.0 hour, and stopping the reaction; cooling the high-pressure reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst from the product by using a magnet, and taking supernatant liquid to analyze the product composition by using gas chromatography. As a result of the experiment, the conversion rate of phenol of the NiCo@C-Surf catalyst without boric acid is only 58.1%, and the selectivity of cyclohexanol is 100%.
Example 6:
the B modified NiCo catalyst is prepared by the following method:
1) Preparation of a catalyst precursor NiCoB@C:
the NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:3 and the ratio of boric acid molar amount to total molar amount of two metal salts of 1.5:5 is placed in ethanol solution for 20 hours at room temperature, surface residues are removed, suction filtration and alternate washing with ethanol and water are carried out for 6 times, and vacuum drying is carried out at 80 ℃ for 12 hours, thus obtaining the pure NiCoB-MOF-74. And (3) placing the obtained pure NiCoB-MOF-74 in a tubular furnace, carrying out pyrolysis in an argon atmosphere, raising the temperature from room temperature to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, and cooling to the room temperature to obtain a carbon-coated nano-scale metal catalyst precursor NiCoB@C.
2) Preparation of NiCoB@C-Surf catalyst:
soaking the obtained NiCoB@C in ethanol solution for 20 hr, removing surface residues, filtering, alternately washing with ethanol and water for 6 times, and vacuum drying at 80deg.CDrying for 12 hours. Placing the obtained NiCoB@C in a tube furnace, and placing in NH 3 Surface treatment is carried out under atmosphere, the temperature is increased to 380 ℃ from room temperature at a heating rate of 3 ℃/min, the temperature is kept for 40 min, and the temperature is reduced to room temperature, so that the NiCoB@C-Surf catalyst is obtained.
The NiCoB@C-Surf catalyst is used for phenol hydrogenation reaction: law of change of phenol hydrogenation performance of catalyst with time
The NiCoB@C-Surf catalyst is used for a cyclohexanol preparation experiment by phenol selective hydrogenation, and a reaction solution system with 3% of phenol mass fraction is prepared by taking a mixture of decalin and isopropanol as a solvent, wherein the mass fraction of isopropanol is 30%. Adding a NiCoB@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leakage of nitrogen, replacing with hydrogen for three times, introducing hydrogen, and stirring at 120 ℃ and 2MPa for reaction, wherein the relationship curve of the phenol conversion rate and the cyclohexanol selectivity over time is shown in fig. 4. As can be seen from FIG. 4, the cyclohexanol selectivity was 100% for each reaction time, indicating that cyclohexanol was the only product. The reaction conversion rate is increased rapidly along with the extension of the reaction time, the reaction time is 0.5 hour, the phenol conversion rate is 63.7%, the reaction time is 1.0 hour, the phenol conversion rate reaches 84.6%, and the phenol conversion rate is 100% after the reaction time is 1.5 hours. The catalytic system of the invention reacts for 1.5 hours at 120 ℃ and 2MPa, thus realizing the complete conversion of phenol, and the catalyst has the characteristics of high hydrogenation activity of phenol, good cyclohexanol selectivity and short reaction time.
Experimental results show that the NiCoB@C-Surf catalyst provided by the invention can achieve the phenol conversion rate of 100% in 1.5 hours, and cyclohexanol is the only reaction product in different reaction times. (1) Compared with the reported single metal catalyst, the activity (100%) of cyclohexanol prepared by phenol hydrogenation after 1.5 hours of reaction is far higher than the experimental result of the reported single metal Ni (phenol conversion rate 23.2%) and Co activity (phenol conversion rate 35.2%) after 12 hours of reaction; (2) Compared with the reported bimetallic NiCo catalyst (reaction time 12 hours), the reaction time is shortened by 10.5 hours. Therefore, the CoNiB@C-Surf catalyst and the catalytic reaction system thereof prepared by the method realize perfect combination of activity and mass transfer, thereby achieving excellent reaction results and having the characteristics of high reaction rate, short reaction time, high activity, good selectivity and the like.
The NiCoB@C-Surf catalyst is used for recycling and regenerating after phenol hydrogenation reaction:
and (3) catalyst recovery:
the catalyst can be recovered conveniently by using a magnet. The solution containing the NiCoB@C-Surf catalyst after the reaction in this example was collected in a glass bottle, the catalyst was sucked by the action of a magnetic field of a magnet (see FIG. 5), the reaction solution was poured out, and the catalyst was recovered. After each reaction, the catalyst was recovered by the same method.
Catalyst regeneration:
the regeneration of the catalyst is simple. Washing the catalyst recovered in the step 1) by using methanol, and then drying in vacuum at 80 ℃ to obtain the regenerated catalyst.
After each reaction, the catalyst was regenerated and reused in the experiments for the selective hydrogenation of phenol to cyclohexanol. The method comprises the steps of taking a mixture of decalin and isopropanol as a solvent, wherein the mass fraction of isopropanol is 30%, and preparing a reaction solution system with the mass fraction of phenol being 3%. Adding a NiCoB@C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, sealing the reaction kettle, detecting the leakage of nitrogen, replacing with hydrogen for three times, introducing hydrogen, and stirring and reacting for 1.5 hours at 120 ℃ and 2MPa, wherein the result is shown in figure 6. After five cycle experiments, the catalytic activity and the selectivity of the target product cyclohexanol have no obvious change, and the catalyst has excellent stability.

Claims (4)

1. A phenol selective hydrogenation method on a B modified NiCo catalyst is characterized by comprising the following steps of: the phenol selective hydrogenation method on the B modified NiCo catalyst comprises the following steps:
(1) Taking NiCoB-MOF-74 as a precursor, soaking the precursor in an alcohol solution, and regulating and controlling the precursor through a pyrolysis process under inert atmosphere and pyrolysis temperature to obtain a carbon-coated nano-scale NiCoB@C catalyst precursor;
the preparation method of the NiCoB-MOF-74 comprises the following steps: adding nickel acetate and cobalt acetate into distilled water to prepare a solution with the total concentration of metal salt of 0.20mol/L, wherein the molar ratio of the nickel acetate to the cobalt acetate is 1:1.2; adding 2, 5-dihydroxyterephthalic acid into tetrahydrofuran, preparing an organic ligand solution with the concentration of 2, 5-dihydroxyterephthalic acid of 0.08mol/L, respectively stirring the two solutions for 10 minutes, mixing, adding boric acid, stirring for 30 minutes, wherein the ratio of the molar quantity of the organic ligand to the total molar quantity of the two metal salts is 1:4, and the ratio of the molar quantity of the boric acid to the total molar quantity of the two metal salts is 1:5; transferring the mixed solution to a polytetrafluoroethylene reaction kettle, putting the mixed solution into a baking oven, carrying out hydrothermal reaction for 60 hours at the temperature of 100 ℃, cooling, carrying out suction filtration, alternately washing with ethanol and water for 6 times, and carrying out vacuum drying for 6 hours at the temperature of 120 ℃ to obtain NiCoB-MOF-74;
soaking in alcohol solution means that the precursor of NiCoB-MOF-74 is soaked in alcohol solution for 8-24 hours, surface residues are removed, suction filtration is carried out, ethanol and water are used for washing for 3-6 times alternately, and vacuum drying is carried out for 8-24 hours at 50-120 ℃;
(2) Soaking NiCoB@C in alcohol solution, and then soaking in NH 3 Treatment under atmosphere, at NH 3 In the atmosphere, the temperature rising rate is 3-5 ℃/min, the temperature is 350-380 ℃, and the treatment is carried out for 30-60 minutes, so as to obtain the high-activity surface modified NiCoB@C-Surf catalyst;
(3) Establishing a catalytic reaction system taking a mixed hydrogen-supplying solvent system as a solvent; the hydrogen-supplying solvent system is a mixed solvent of one of decalin, tetrahydronaphthalene and dihydronaphthalene and isopropanol, wherein the mass fraction of the isopropanol is 20-40%; the mass fraction of phenol in the hydrogen-supplying solvent reaction system is 2-5%; the addition amount of the NiCoB@C-Surf catalyst is that the mass ratio of the NiCoB@C-Surf catalyst to the phenol solution is 0.0005-0.002:1;
(4) Under certain hydrogen partial pressure and reaction temperature, the activity of the catalyst is improved based on (1), (2) and (3), the adsorption effect of phenol on the surface of the catalyst is enhanced, the rapid selective hydrogenation of phenol on the NiCoB@C-Surf catalyst is accelerated, the hydrogen partial pressure is 2-3 MPa at the reaction temperature of 80-120 ℃, the reaction time is 1.5-2 hours, the phenol is completely converted into cyclohexanol, and the catalyst can be recycled after separation.
2. The method for selectively hydrogenating phenol on a B-modified NiCo catalyst according to claim 1, wherein the preparation of the NiCoB@C catalyst precursor by regulating and controlling pyrolysis conditions under inert atmosphere means that the NiCoB-MOF-74 precursor is pyrolyzed under argon atmosphere, the heating rate is 3-5 ℃/min, the pyrolysis temperature is 500-600 ℃, and the pyrolysis time is 2-3 hours to obtain the NiCoB@C catalyst precursor.
3. The method for selectively hydrogenating phenol on a B-modified NiCo catalyst according to claim 1, wherein the immersing of nicob@c in an alcohol solution means immersing nicob@c in an alcohol solution for 8 to 24 hours, removing surface residues, suction-filtering, washing with ethanol and water alternately for 3 to 6 times, and vacuum-drying at 50 to 120 ℃ for 8 to 24 hours.
4. The selective hydrogenation method for phenol on a B-modified NiCo catalyst according to claim 1, wherein the catalyst separation method is magnetic separation, and the activity and selectivity of the separated catalyst are unchanged after the separated catalyst is recycled for 5 times through reaction separation.
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