CN113336626A - Method for selective hydrogenation of phenol on B modified NiCo catalyst - Google Patents

Method for selective hydrogenation of phenol on B modified NiCo catalyst Download PDF

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CN113336626A
CN113336626A CN202110666579.5A CN202110666579A CN113336626A CN 113336626 A CN113336626 A CN 113336626A CN 202110666579 A CN202110666579 A CN 202110666579A CN 113336626 A CN113336626 A CN 113336626A
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catalyst
nicob
phenol
surf
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CN113336626B (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
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a method for selectively hydrogenating phenol on a B modified NiCo catalyst, which comprises the following steps: (1) soaking NiCoB-MOF-74 serving as a precursor in an alcohol solution, and regulating and controlling a pyrolysis process to obtain a carbon-coated nanoscale catalyst precursor NiCoB @ C; (2) soaking NiCoB @ C in alcoholic solution, and then soaking in NH3Processing under atmosphere to obtain a high-activity surface modified NiCoB @ C-Surf catalyst; (3) establishing a catalytic reaction system with a mixed hydrogen donor solvent system as a solvent; (4) based on the (1), (2) and (3), the activity of the catalyst is improved, the adsorption effect of phenol on the surface of the catalyst is strengthened, the selective hydrogenation speed of phenol on the NiCoB @ C-Surf catalyst is accelerated, and the phenol is completely converted into cyclohexanol after reacting for 1.5-2 hours. The invention has low cost, high reaction speed and short reaction time.

Description

Method for selective hydrogenation of phenol on B modified NiCo catalyst
The technical field is as follows:
the invention belongs to the technical field of catalysis, and particularly relates to a selective hydrogenation method for phenol on a B modified NiCo catalyst.
Background art:
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. The cyclohexanol can also be used for preparing 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 is relatively low in cost, but the reaction conditions are severe, the yield is low, and the separation steps are complicated. 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 catalytic activity for phenol hydrogenation, but the 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 an advantage in price have been receiving attention in the reaction of hydrogenating phenol to produce cyclohexanol. However, the prior 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-efficiency transition metal catalyst with the cyclohexanol selectivity of 100% by high-performance phenol hydrogenation is of great significance.
Document [ Aiqin Li: high hly selective hydrogenation of phenol to cyclic acetal over MOF-derived non-non Co-Ni @ NC catalysts, doi http:// dx. doi. org/10.1016/j. ces.2017.03.027]Using nitrate of transition metals Ni and Co, organic ligand of terephthalic acid and triethyldiamine to synthesize MOF material in N, N-dimethylformamide solvent, and passing through 600oAnd C, preparing Ni @ NC-600 and Co @ NC-600 catalysts by pyrolysis. The reaction is carried out for 12 hours at 100 ℃ and 0.8MPa by taking isopropanol as a solvent, and the phenol conversion rates of the Ni @ NC-600 catalyst and the Co @ NC-600 catalyst are respectively 23.2 percent and 35.2% cyclohexanol selectivity>99.9 percent. However, the single metal catalyst has a problem that the reaction time is long (12 hours) and the conversion rate of phenol is too low. And then the bimetallic NiCo @ NC-600 catalyst is prepared by the catalyst, and the reaction is carried out for 12 hours at 100 ℃ and 0.8MPa by taking isopropanol as a solvent, wherein the conversion rate and the cyclohexanol selectivity are both more than 99.9 percent, but the reaction time is still very long (12 hours). The Chinese patent application with the publication number of CN104447209A, namely a Co and Ni catalyst loaded by a porous carbon material obtained by reacting glucosamine salt, melamine and cobalt or nickel salt, is used for preparing cyclohexanol by hydrogenating phenol, and has the reaction temperature of 150 at 3MPaoC, the conversion rate reaches 100%, the cyclohexanol selectivity is over 99%, but the problems of too long reaction time (12-30 hours) and slow reaction rate exist. Therefore, the development of the catalyst for preparing cyclohexanol from phenol, which takes the transition metal with low price as an active component, has 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 feedstock is another key 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, and the high conversion rate and selectivity can not be achieved. The invention provides a method for preparing 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 size, the dispersity and the surface property of metal nano particles and the hydrogen supply capacity of the reaction system are regulated and controlled to improve the hydrogenation catalytic activity and the selectivity through the selection of the precursor of the catalyst, a preparation route, preparation conditions and the design of the catalytic reaction system; (2) the solubility 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. The perfect combination of catalytic activity and phenol mass transfer realizes excellent phenol hydrogenation catalytic effect.
The invention content is as follows:
the invention aims to provide a selective hydrogenation method for phenol on a B modified NiCo catalyst, and the B modified NiCo catalyst and a catalytic reaction system thereof provide a method for preparing cyclohexanol by efficiently hydrogenating phenol, and are used for solving the problems of low conversion rate and long reaction time of a catalyst for preparing cyclohexanol by hydrogenating phenol in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for selectively hydrogenating phenol on the B modified NiCo catalyst comprises the following steps:
(1) soaking NiCoB-MOF-74 serving as a precursor in an alcohol solution, and regulating and controlling a pyrolysis process under an inert atmosphere and a pyrolysis temperature to obtain a carbon-coated nanoscale catalyst precursor NiCoB @ C;
(2) soaking NiCoB @ C in alcoholic solution, and then soaking in NH3Processing under atmosphere to obtain a high-activity surface modified NiCoB @ C-Surf catalyst;
(3) establishing a catalytic reaction system with a mixed hydrogen donor 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 strengthened, the selective hydrogenation speed of phenol on the NiCoB @ C-Surf catalyst is accelerated, the phenol is completely converted into cyclohexanol at the reaction temperature of 80-120 ℃, the hydrogen partial pressure of 2-3 MPa, the reaction time of 1.5-2 hours, and the catalyst can be recycled after being separated.
In the NiCoB-MOF-74 precursor in the scheme, 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 two metal salts is 1-2: 5, and the added B is boric acid.
The soaking treatment in the alcoholic solution in the scheme refers to soaking the NiCoB-MOF-74 precursor in an ethanol solution for 8-24 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 3-6 times, and performing vacuum drying at 50-120 ℃ for 8-24 hours.
In the scheme, when the catalyst precursor NiCoB @ C is prepared by regulating and controlling pyrolysis conditions under inert atmosphere: and pyrolyzing the NiCoB-MOF-74 precursor in an argon atmosphere at the heating rate of 3-5 ℃/min, the pyrolysis temperature of 500-600 ℃ and the pyrolysis time of 2-3 hours to obtain a catalyst precursor NiCoB @ C.
In the scheme, the NiCoB @ C is soaked in the alcohol solution for 8-24 hours, the surface residues are removed, the NiCoB @ C is subjected to suction filtration, washed for 3-6 times by using ethanol and water alternately, and dried for 8-24 hours in vacuum at the temperature of 50-120 ℃.
In NH as described in the above schemes3Treatment under an atmosphere means under NH3And under the atmosphere, treating for 30-60 minutes at the temperature rising rate of 3-5 ℃/min and the temperature of 350-380 ℃ to obtain the NiCoB @ C-Surf catalyst.
The hydrogen donor solvent system in the scheme is a mixed solvent of isopropanol and one of decahydronaphthalene, tetrahydronaphthalene and dihydronaphthalene, wherein the mass fraction of the isopropanol is 20-40%.
The mass fraction of the phenol in the hydrogen donor solvent reaction system in the scheme 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 not changed after the catalyst is recycled 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 bimetal as active components, and has the characteristics of low cost, high reaction rate, short reaction time, high activity, good selectivity and the like.
(2) The method for preparing cyclohexanol by selective hydrogenation of phenol provided by the invention 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 line, selecting a metal organic framework NiCoB-MOF-74 as a catalyst precursor, and restricting metal nano particles in a narrow range by virtue of strong coordination between metal and organic ligands and the domain limiting effect of MOF to prevent the aggregation and growth of the particles so as to expose more metal active sites; (b) in the preparation method of the catalyst, the catalyst is prepared,through boric acid modification, the heteroatom B is doped in the carbon substrate of the catalyst, so that the positive charge density of adjacent carbon atoms is increased, the induced charge is uneven, and the H of the metal is improved2Activating the cracking capacity; the metal Ni and the metal Co in the catalyst have an isolation effect, so that the agglomeration of metal particles can be further inhibited; electrons are transferred from metal Ni to Co, and the bimetal has higher activity due to the synergistic effect between Ni and Co; NiCoB-MOF-74 is pretreated to remove impurities and improve the activity of the catalyst; the catalyst is subjected to surface modification through alcohol and ammonia treatment, and the electron distribution and surface property on the surface of the catalyst are changed, so that the phenol hydrogenation activity and the cyclohexanol selectivity are improved; (c) in the selection of the reaction system, the invention uses a mixed system of one of decalin, tetrahydronaphthalene and dihydronaphthalene and isopropanol as a solvent to form a catalytic reaction system, and 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 selective hydrogenation of phenol provided by the invention has the characteristics of high reaction speed of phenol hydrogenation and short reaction time, and the catalyst and the catalytic reaction system constructed by the invention accelerate the time for the reactant phenol to reach the active site of the catalyst: the precursor NiCoB-MOF-74 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-OH groups which can promote the adsorption of reactant phenol on the surface of the catalyst through hydrogen bond interaction with-OH groups in phenol, and the time required for the reactant to reach the active site of the catalyst is shortened; (b) the B in the catalyst carbon substrate reacts with the 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 quickly reaches the surface of the catalyst. (c) The invention provides a catalytic reaction system which uses a mixed system of isopropanol and one of decahydronaphthalene, tetrahydronaphthalene and dihydronaphthalene as a solvent, and the solvent has good solubility to phenol and can promote the sufficient contact between phenol and a catalyst; (d) the catalyst is subjected to surface modification through alcohol treatment and ammonia gas treatment, so that the surface property of the catalyst is changed, and the adsorption of a reactant phenol on an active site of the catalyst is accelerated.
(4) The method for preparing cyclohexanol by selective hydrogenation of phenol provided by the invention can achieve the conversion rate of phenol of 100% and the selectivity of cyclohexanol of 100% within 2 hours. Compared with the prior art (12 hours), the method has the characteristic of short reaction time on the premise that the conversion rate of phenol and the selectivity of cyclohexanol are both 100 percent. This is mainly due to the high activity of the NiCoB @ C-Surf catalyst of the present invention, which rapidly provides the phenol needed for the reaction to reach the active sites on the surface of the catalyst by enhancing the adsorption of phenol on the surface of the catalyst. The method aims to achieve the aims of high phenol hydrogenation activity, good cyclohexanol selectivity, short reaction time, high activity and quick mass transfer. Therefore, the invention realizes the perfect combination of activity and mass transfer, thereby achieving excellent reaction result.
(5) In the catalyst provided by the invention, as the active phase is carbon-coated NiCo bimetallic nanoparticles, the active component is protected by a carbon layer, and the catalyst has magnetism and can be separated from a reaction product by a magnet. Therefore, the catalyst has excellent stability on the surface, convenient recovery and good reusability.
Description of the drawings:
FIG. 1 is a schematic diagram of the synthesis scheme of NiCoB @ C-Surf catalyst.
FIG. 2 is an XRD pattern of 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 representation of NiCoB @ C-Surf catalyst recovery.
FIG. 6 is a graph of the reusability of NiCoB @ C-Surf catalysts.
The specific implementation mode is as follows:
the invention will be further described with reference to the accompanying drawings in which:
example 1:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
the synthetic route of the NiCoB @ C-Surf catalyst is shown in figure 1, and firstly, a catalyst precursor NiCoB @ C is synthesized, and the synthesis method specifically comprises the following steps:
soaking NiCoB-MOF-74 in an ethanol solution at room temperature for 8 hours, removing surface residues, carrying out suction filtration, alternately washing with ethanol and water for 6 times, and carrying out vacuum drying at 60 ℃ for 18 hours to obtain pure NiCoB-MOF-74. And (3) putting the pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 550 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 2 hours, and reducing the temperature to room temperature to obtain a carbon-coated nano-scale metal catalyst precursor NiCoB @ C.
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 0.20 mol/L, wherein the molar ratio of the nickel acetate to the cobalt acetate is 1: 1.2; adding 2, 5-dihydroxyterephthalic acid into a solvent in tetrahydrofuran to prepare an organic ligand solution with the concentration of the 2, 5-dihydroxyterephthalic acid of 0.08 mol/L. Stirring the two solutions for 10 minutes respectively, then mixing, adding boric acid, and stirring for 30 minutes, wherein the ratio of the molar amount of the organic ligand to the total molar amount of the two metal salts is 1:4, and the ratio of the molar amount of the boric acid to the total molar amount of the two metal salts is 1: 5; and transferring the mixed solution to a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into an oven, carrying out hydrothermal reaction for 60 hours at 100 ℃, cooling, carrying out suction filtration, alternately washing with ethanol and water for 6 times, and carrying out vacuum drying for 6 hours at 120 ℃ 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 to remove surface residues, suction-filtered, washed with ethanol and water alternately 6 times, and vacuum-dried at 60 ℃ for 18 hours. The NiCoB @ C thus obtained was placed in a tube furnace in NH3And (4) treating under an atmosphere, raising the temperature from room temperature to 380 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 60 min, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
XRD characterization of NiCoB @ C-Surf catalyst:
XRD characterization is carried out on the NiCoB @ C-Surf catalyst obtained in the step 2), and the active phase in the catalyst is analyzed and tested, so that the catalyst shows that characteristic peaks of metal Ni and Co alloys 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 a single metal alloy nano particle is present in the catalyst, and no other impure phases are present.
Example 2:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
soaking NiCoB-MOF-74 in an ethanol solution at room temperature for 24 hours, removing surface residues, carrying out suction filtration, alternately washing with ethanol and water for 4 times, and carrying out vacuum drying at 120 ℃ for 8 hours to obtain pure NiCoB-MOF-74. And (3) putting the pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3 hours, and reducing the temperature to room temperature to obtain a carbon-coated nano-scale metal catalyst precursor NiCoB @ C.
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; adding 2, 5-dihydroxyterephthalic acid into a solvent in tetrahydrofuran to prepare an organic ligand solution with the concentration of the 2, 5-dihydroxyterephthalic acid of 0.05 mol/L. Stirring the two solutions for 10 minutes respectively, then mixing, adding boric acid, and stirring for 30 minutes, wherein the ratio of the molar amount of the organic ligand to the total molar amount of the two metal salts is 1:8, and the ratio of the molar amount of the boric acid to the total molar amount of the two metal salts is 2: 5; and transferring the mixed solution to a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into an oven, carrying out hydrothermal reaction for 45 hours at 120 ℃, cooling, carrying out suction filtration, alternately washing with ethanol and water for 3 times, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain NiCoB-MOF-74.
2) Preparation of NiCoB @ C-Surf catalyst:
putting the NiCoB @ C in 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 hoursThen (c) is performed. The NiCoB @ C thus obtained was placed in a tube furnace in NH3And (4) treating under an atmosphere, raising the temperature from room temperature to 350 ℃ at a temperature raising rate of 5 ℃/min, keeping the temperature for 50 min, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
TEM characterization of NiCoB @ C-Surf catalyst:
TEM characterization of the NiCoB @ C-Surf catalyst obtained in step 2) is carried out, the size of an active phase in the catalyst is analyzed and tested, and the result is shown in figure 3, the metal nanoparticles are uniformly distributed and do not obviously aggregate, and the carbon-coated nanoparticles can be clearly seen from a large-magnification image. In the catalyst, the average particle size of the metal nanoparticles is only about 3.0-5.0 nm. The small size and uniform dispersion of the metal nanoparticles are one of the keys that the catalyst has high phenol conversion rate and can be converted into cyclohexanol in short time.
Example 3:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
soaking NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:1.5 and the ratio of the molar amount of boric acid to the total molar amount of two metal salts of 1.5:5 in an ethanol solution at room temperature for 16 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 3 times, and performing vacuum drying at 120 ℃ for 8 hours to obtain pure NiCoB-MOF-74. And (3) putting the pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 550 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3 hours, and reducing the temperature to 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 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; the NiCoB @ C thus obtained was placed in a tube furnace in NH3And (3) processing in the atmosphere, raising the temperature from room temperature to 360 ℃ at a temperature rise rate of 5 ℃/min, keeping the temperature for 40 minutes, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
The NiCoB @ C-Surf catalyst obtained in this example was used in the phenol hydrogenation reaction:
the NiCoB @ C-Surf catalyst is used for the experiment of preparing cyclohexanol by selective hydrogenation of phenol. 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 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 by nitrogen, replacing the reaction kettle by hydrogen for three times, introducing hydrogen, stirring and reacting for 2 hours at 80 ℃ and 3MPa, and stopping the reaction; cooling the reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst and the product by using a magnet, and taking supernatant liquid to analyze the composition of the product by using gas chromatography. The experimental results show that the conversion rate of phenol is 100% and the selectivity of cyclohexanol is 100%.
Example 4:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
soaking NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:2 and the ratio of the molar amount of boric acid to the total molar amount of two metal salts of 1.7:5 in an ethanol solution at room temperature for 12 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 3 times, and performing vacuum drying at 120 ℃ for 8 hours to obtain pure NiCoB-MOF-74. And (3) putting the pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 550 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 3 hours, and reducing the temperature to 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 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; the NiCoB @ C thus obtained was placed in a tube furnace in NH3And (4) processing in the atmosphere, raising the temperature from room temperature to 350 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 60 minutes, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
The NiCoB @ C-Surf catalyst obtained in this example was used in the phenol hydrogenation reaction:
the NiCoB @ C-Surf catalyst is used for the experiment of preparing cyclohexanol by selective hydrogenation of phenol. The mixture of dihydronaphthalene and isopropanol is used as a solvent, wherein the mass fraction of the isopropanol is 40%, and a reaction solution system with the mass fraction of phenol of 2% is prepared. Adding 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 by nitrogen, replacing the reaction kettle with hydrogen for three times, introducing hydrogen, stirring and reacting for 1.5 hours at 100 ℃ and 3MPa, and stopping the reaction; cooling the reaction kettle to room temperature, discharging hydrogen, pouring out the reaction mixture, separating the catalyst and the product by using a magnet, and taking supernatant liquid to analyze the composition of the product by using gas chromatography. The experimental results show that the conversion rate of phenol is 100% and the selectivity of cyclohexanol is 100%.
Example 5:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
soaking NiCoB-MOF-74 prepared at the molar ratio of nickel to cobalt of 1:3 and the ratio of the molar amount of boric acid to the total molar amount of two metal salts of 1.5:5 in an ethanol solution for 20 hours at room temperature, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 80 ℃ for 12 hours to obtain pure NiCoB-MOF-74. And putting the obtained pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and reducing the temperature to room temperature to obtain a carbon-coated nanoscale metal catalyst precursor NiCoB @ C.
2) Preparation of NiCoB @ C-Surf catalyst:
and soaking the obtained NiCoB @ C in an ethanol solution for 20 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 80 ℃ for 12 hours. The NiCoB @ C thus obtained was placed in a tube furnace in NH3And performing surface treatment in the atmosphere, raising the temperature from room temperature to 380 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 40 min, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
The effect of the addition of boric acid on the hydrogenation performance of the catalyst phenol was investigated by this example:
to investigate the effect of boric acid, the procedure was followed completely in steps 1) and 2) to obtain NiCo @ C-Surf catalyst, except that in step 1) a nickel to cobalt molar ratio of 1:3 NiCoB-MOF-74 was used instead of B.
Under the same reaction conditions, the NiCo @ C-Surf catalyst and the NiCoB @ C-Surf prepared in the example are respectively used for the experiment for preparing cyclohexanol by phenol selective hydrogenation:
experiment 1: the mixture of decalin and isopropanol is used as a solvent, wherein the mass fraction of the isopropanol is 30%, and a reaction solution system with the mass fraction of phenol being 3% is prepared. Adding NiCoB @ C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leakage by nitrogen, replacing the mixture by hydrogen for three times, introducing hydrogen, reacting for 1.0 hour under the conditions of 120 ℃ and 2MPa by stirring, and stopping the reaction; cooling the high-pressure reaction kettle to room temperature, discharging hydrogen, pouring out a reaction mixture, separating the catalyst and a product by using a magnet, and taking supernatant liquid to analyze the composition of the product by using gas chromatography. The experiment result shows that the NiCoB @ C-Surf catalyst has the phenol conversion rate of 84.6 percent and the cyclohexanol selectivity of 100 percent.
Experiment 2: the mixture of decalin and isopropanol is used as a solvent, wherein the mass fraction of the isopropanol is 30%, and a reaction solution system with the mass fraction of phenol being 3% is prepared. Adding NiCo @ C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leakage by nitrogen, replacing the mixture by hydrogen for three times, introducing hydrogen, reacting for 1.0 hour under stirring at 120 ℃ and 2MPa, and stopping the reaction; cooling the high-pressure reaction kettle to room temperature, discharging hydrogen, pouring out a reaction mixture, separating the catalyst and a product by using a magnet, and taking supernatant liquid to analyze the composition of the product by using gas chromatography. As a result, the phenol conversion rate of the NiCo @ C-Surf catalyst without adding boric acid is only 58.1 percent, and the cyclohexanol selectivity is 100 percent.
Example 6:
the B modified NiCo catalyst is prepared by the following method:
1) preparation of catalyst precursor NiCoB @ C:
and (2) at room temperature, putting NiCoB-MOF-74 prepared under the conditions that the molar ratio of nickel to cobalt is 1:3, and the ratio of the molar amount of boric acid to the total molar amount of two metal salts is 1.5:5 in an ethanol solution for 20 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 80 ℃ for 12 hours to obtain pure NiCoB-MOF-74. And putting the obtained pure NiCoB-MOF-74 into a tube furnace, pyrolyzing the pure NiCoB-MOF-74 in an argon atmosphere, raising the temperature from room temperature to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and reducing the temperature to room temperature to obtain a carbon-coated nanoscale metal catalyst precursor NiCoB @ C.
2) Preparation of NiCoB @ C-Surf catalyst:
and soaking the obtained NiCoB @ C in an ethanol solution for 20 hours, removing surface residues, performing suction filtration, alternately washing with ethanol and water for 6 times, and performing vacuum drying at 80 ℃ for 12 hours. The NiCoB @ C thus obtained was placed in a tube furnace in NH3And performing surface treatment in the atmosphere, raising the temperature from room temperature to 380 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 40 min, and reducing the temperature to room temperature to obtain the NiCoB @ C-Surf catalyst.
The NiCoB @ C-Surf catalyst is used for a phenol hydrogenation reaction: law of change of phenol hydrogenation performance of catalyst with time
The NiCoB @ C-Surf catalyst is used for an experiment for preparing cyclohexanol by phenol selective hydrogenation, a mixture of decalin and isopropanol is used as a solvent, wherein the mass fraction of the isopropanol is 30%, and a reaction solution system with the mass fraction of the phenol being 3% is prepared. Adding NiCoB @ C-Surf catalyst, wherein the mass ratio of the catalyst to the phenol solution is 0.002:1, detecting the leakage by nitrogen, replacing the mixture by hydrogen for three times, introducing hydrogen, stirring and reacting at 120 ℃ and 2MPa, and obtaining a relation curve of the change of the phenol conversion rate and the cyclohexanol selectivity along with time, wherein the relation curve is shown in figure 4. As can be seen from FIG. 4, cyclohexanol selectivity was 100% at each reaction time, indicating cyclohexanol as the sole 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 percent, the reaction time is 1.0 hour, the phenol conversion rate reaches 84.6 percent, and the phenol conversion rate is 100 percent after the reaction time is 1.5 hours. The catalyst system of the invention reacts for 1.5 hours at 120 ℃ and 2MPa, realizes the complete conversion of phenol, and has the characteristics of high phenol hydrogenation activity, 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% within 1.5 hours, and cyclohexanol is the only reaction product at different reaction times. (1) Compared with the reported single metal catalyst, the activity (100%) of preparing cyclohexanol by hydrogenating phenol after 1.5 hours of reaction is far higher than the reported activities (35.2% of phenol conversion) of single metal Ni and Co for 12 hours of reaction; (2) the reaction time was 10.5 hours shorter than that reported for bimetallic NiCo catalysts (reaction time 12 hours). Therefore, the CoNiB @ C-Surf catalyst and the catalytic reaction system thereof prepared by the invention realize perfect combination of activity and mass transfer, thereby achieving excellent reaction result 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 recovering and regenerating after phenol hydrogenation reaction:
catalyst recovery:
the catalyst can be conveniently recovered by using a magnet. The solution containing NiCoB @ C-Surf catalyst after the reaction in this example was collected in a glass bottle, and the catalyst was attracted by the magnetic field of a magnet (see FIG. 5), and the reaction solution was poured out to recover the catalyst. After each reaction, the catalyst was recovered in the same manner.
Catalyst regeneration:
the regeneration of the catalyst is simple. Washing the catalyst recovered in the step 1) by using methanol, and then drying the catalyst in vacuum at the temperature of 80 ℃ to obtain the regenerated catalyst.
After each reaction, the catalyst was regenerated and reused for the experiment of selective hydrogenation of phenol to cyclohexanol. The mixture of decalin and isopropanol is used as a solvent, wherein the mass fraction of the isopropanol is 30%, and a reaction solution system with the mass fraction of phenol being 3% is prepared. Adding 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 by nitrogen, replacing three times by hydrogen, introducing hydrogen, and stirring and reacting at 120 ℃ and 2MPa for 1.5 hours, wherein the result is shown in figure 6. After five times of circulation experiments, the catalytic activity and the selectivity of the target product cyclohexanol are not obviously changed, and the catalyst is proved to have excellent stability.

Claims (10)

1. A method for selectively hydrogenating phenol on a B modified NiCo catalyst is characterized by comprising the following steps: the method for selectively hydrogenating phenol on the B modified NiCo catalyst comprises the following steps:
(1) soaking NiCoB-MOF-74 serving as a precursor in an alcohol solution, and regulating and controlling a pyrolysis process under an inert atmosphere and a pyrolysis temperature to obtain a carbon-coated nanoscale NiCoB @ C catalyst precursor;
(2) soaking NiCoB @ C in alcoholic solution, and then soaking in NH3Processing under atmosphere to obtain a high-activity surface modified NiCoB @ C-Surf catalyst;
(3) establishing a catalytic reaction system with a mixed hydrogen donor 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 strengthened, the rapid selective hydrogenation of phenol on a NiCoB @ C-Surf catalyst is accelerated, the phenol is completely converted into cyclohexanol at the reaction temperature of 80-120 ℃, the hydrogen partial pressure of 2-3 MPa, the reaction time of 1.5-2 hours, and the catalyst can be recycled after being separated.
2. The method for selective hydrogenation of phenol on B modified NiCo catalyst of claim 1, wherein in the NiCoB-MOF-74 precursor, the molar ratio of nickel salt and cobalt salt is 1: 1.2-4, the ratio of the molar amount of B to the total molar amount of two metal salts is 1-2: 5, and the added B is boric acid.
3. The method for selective hydrogenation of phenol on a B modified NiCo catalyst according to claim 1, wherein the soaking treatment in an alcohol solution is to soak a NiCoB-MOF-74 precursor in an alcohol solution for 8-24 hours, remove surface residues, pump-filter, wash with alcohol and water alternately for 3-6 times, and vacuum-dry at 50-120 ℃ for 8-24 hours.
4. The method for selectively hydrogenating phenol on the B modified NiCo catalyst according to claim 1, wherein the preparation of the NiCoB @ C catalyst precursor in the inert atmosphere by regulating pyrolysis conditions means that the NiCoB-MOF-74 precursor is pyrolyzed in an argon atmosphere at a temperature rise rate of 3-5 ℃/min, a pyrolysis temperature of 500-600 ℃ and a pyrolysis time of 2-3 hours to obtain the NiCoB @ C catalyst precursor.
5. The method for selective hydrogenation of phenol on B modified NiCo catalyst of claim 1, wherein the soaking NiCoB @ C in alcohol solution is to soak NiCoB @ C in alcohol solution for 8-24 hours, remove surface residues, pump filter, wash with ethanol and water for 3-6 times alternately, and vacuum dry at 50-120 ℃ for 8-24 hours.
6. The method of claim 1, wherein said selective hydrogenation of phenol on a B modified NiCo catalyst is carried out on NH3Treatment under an atmosphere means under NH3And under the atmosphere, treating for 30-60 minutes at the temperature rising rate of 3-5 ℃/min and the temperature of 350-380 ℃ to obtain the NiCoB @ C-Surf catalyst.
7. The method for selectively hydrogenating phenol on the B modified NiCo catalyst according to claim 1, wherein the hydrogen donor solvent system is a mixed solvent of isopropanol and one of decahydronaphthalene, tetrahydronaphthalene and dihydronaphthalene, wherein the mass fraction of the isopropanol is 20-40%.
8. The method for selectively hydrogenating phenol on the B modified NiCo catalyst according to claim 1, wherein the mass fraction of the phenol in the hydrogen donor solvent reaction system is 2-5%.
9. The method for selective hydrogenation of phenol on a B modified NiCo catalyst of claim 1, wherein the amount of NiCoB @ C-Surf catalyst added is such that the mass ratio of NiCoB @ C-Surf catalyst to phenol solution is 0.0005-0.002: 1.
10. The method for selective hydrogenation of phenol on B modified NiCo catalyst of claim 1, wherein said catalyst separation method is magnetic separation, and the activity and selectivity of the separated catalyst is unchanged after the separated catalyst is recycled for 5 times through reaction separation.
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