CN110694656A - Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion - Google Patents
Hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cyclane through guaiacol conversion Download PDFInfo
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Abstract
The invention relates to a hydrotalcite-based nickel phosphide catalyst and application thereof in preparation of cycloalkane by guaiacol conversion. The structural formula of the catalyst is represented as Ax‑Niy-P, wherein x is greater than 0 and less than or equal to 10 and y is greater than 0 and less than or equal to 10; a is one or two +3 valence metals of Al, Fe and Ce. The guaiacol hydrogenolysis reaction is carried out in a batch high-pressure reaction kettle, the reaction medium is an organic solvent which does not participate in the reaction, the internal standard substance of the reaction is n-dodecane, the mass ratio of the substrate to the catalyst is 1:1-10:1, the initial pressure of hydrogen filled in the reaction kettle at room temperature is 2-6MPa, the temperature is increased to 150-300 ℃, the reaction time is 1-5h, and the stirring revolution is 1000 r/min. The conversion rate of lignin monomer guaiacol is high, the cycloparaffin in the product is used as the main product, the catalyst has strong selectivity to the product, and the main product is used in industryHas wide application and good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of novel catalytic material application, and further discloses application of a novel catalyst in the field of preparation of high-added-value fine chemicals through catalytic conversion of biomass. In particular to the application of a hydrotalcite-based nickel phosphide catalyst in the preparation of cyclane through the conversion of guaiacol.
Background
The reduction of fossil energy reserves such as coal, petroleum and the like causes the world to face a huge energy crisis, and the reasonable development and utilization of renewable energy are effective methods for solving the crisis. Biomass has received increasing attention as a renewable energy source due to its vast reserves and renewable properties. Among the components of the woody biomass, the lignin is rich in content and wide in source, and is a complex natural high molecular compound raw material with the content second to that of cellulose in the nature. However, lignin is also the most complex structure in woody biomass, and is formed by connecting various units with different benzene ring structures through C-C bonds and C-O bonds, so that a complicated three-dimensional polymer compound is formed. The high oxygen content limits further utilization, and active reaction among small molecules brings certain difficulty in tracking the lignin conversion pathway. Therefore, it is necessary and meaningful to obtain more efficient lignin conversion rules to fully utilize lignin and its derivative compounds based on the reaction of its model compound guaiacol.
Hydrodeoxygenation (HDO) of guaiacol is considered to be one of the effective methods for producing high value-added chemicals and biofuels. Various guaiacol hydrodeoxygenation catalysts have been investigated in the past exploration, including noble metal catalysts, transition metal sulfides, transition metal phosphides, and the like. Noble metal catalysts can activate molecular hydrogen efficiently under mild conditions with high catalytic conversion activity, but their expensive cost limits their large-scale industrial application. Meanwhile, noble metals on non-acidic supports generally exhibit a strong propensity for the demethoxylation of guaiacol and the hydrogenation of aromatic rings, but also lack the ability to fully deoxygenate guaiacol to benzene and cyclohexane. The transition metal sulfide catalyst has good hydrodeoxygenation performance and is widely applied to the catalytic hydrogenation process of petroleum refining. But the sulfide catalyst faces the problem of sulfur loss in the process of biomass catalytic conversion, so that the activity of the catalyst is obviously reduced. Transition metal phosphide catalysts also have high catalytic activity and are widely studied. The metal phosphide has high catalytic activity in Hydrodesulfurization (HDS) and Hydrodenitrogenation (HDN), excellent activity in Hydrodeoxygenation (HDO), low preparation cost and great industrial application potential.
Leading pair of Ni2The research on the HDO reaction of P on biomass is not few, and a series of progresses are made, but a few problems exist, such as the requirement on reaction conditions is high, the reaction temperature is generally required to be 300-350 ℃, the energy consumption is large, and great resistance is brought to practical application. Ni of hydrotalcite structure described in the patent2The P catalyst has good low-temperature activity, and the yield of the main product cyclohexane reaches 80.6% at the reaction temperature of 250 ℃, so that the problems are well solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a nickel phosphide catalyst, a preparation method and application thereof, and solves the problems of high lignin conversion cost and low product yield in the prior art.
The technical scheme of the invention is as follows:
a hydrotalcite-based nickel phosphide catalyst with a structural formula of Ax-Niy-P, wherein x is greater than 0 and less than or equal to 10 and y is greater than 0 and less than or equal to 10; a is one or two +3 valence metals of Al, Fe and Ce.
The preparation method of the nickel phosphide catalyst with the hydrotalcite structure comprises the following steps:
a) adding soluble salt containing Ni and soluble salt containing metal element A into deionized water according to a molar ratio, then adding ammonium fluoride and urea, stirring and dissolving to form clear solution, putting the solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction;
b) after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, and drying the precipitate in a vacuum drying oven;
c) grinding the dried precursor obtained in the step b) in a mortar to make the precursor fine and uniform, and then placing the precursor in a muffle furnace for roasting to form an oxide of a corresponding metal;
d) calcining the metal oxide obtained in c) in H2And N2Carrying out reduction reaction in the atmosphere of (1) to obtain a corresponding metal or metal oxide chimera;
e) taking out and weighing the metal chimera obtained in the step d), weighing the red phosphorus simple substance according to the molar ratio, grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar uniformly, and then placing the mixture in a H2And N2Carrying out a second reduction reaction in the atmosphere of (3); obtaining the corresponding nickel phosphide catalyst with the hydrotalcite structure.
The metal soluble salt in the step a) can be nitrate, citrate, chloride, sulfate or oxalate; the molar ratio of Ni to the + 3-valent metal is 1: 1-8: 1; the molar quantity of the Ni metal salt and the molar concentration of the + 3-valent metal salt are within 0.025-0.075 mol/L, the molar concentration of the ammonium fluoride is within 0.1-0.5 mol/L, and the molar concentration of the urea is within 0.25-1.25 mol/L;
the temperature of the hydrothermal reaction in the step a) is 100-150 ℃, and the time is 15-20 h.
The temperature of the drying in the step b) is 60-100 ℃, and the time is 10-12 hours.
In the step c), the roasting temperature of the muffle furnace is 400-600 ℃, and the time is 3-5 hours.
H reduced in step d) is2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400 DEG CThe temperature is 500 ℃ below zero, the time is 3-5 h, and the heating rate is 2-5 ℃/min.
In the step e), Ni/P is 2-3, and H is generated during reduction2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400-500 ℃, the time is 3-5 h, and the heating rate is 2-5 ℃/min.
The application of the hydrotalcite-structured nickel phosphide catalyst in the guaiacol hydrogenolysis reaction is as follows: the guaiacol hydrogenolysis reaction is carried out in a batch high-pressure reaction kettle, the reaction medium is an organic solvent which does not participate in the reaction, the reaction internal standard substance is n-dodecane, the concentration of the reaction raw material is 0.05-0.15mol/L, the mass ratio of the substrate to the catalyst is 1:1-10:1, the initial pressure of hydrogen filled in the reaction kettle at room temperature is 2-6MPa, the temperature is increased to the reaction temperature of 150 ℃ and 300 ℃, the reaction time is 1-5h, and the stirring revolution is 1000 r/min.
The organic solvent is methylcyclohexane, decalin, methanol or ethanol.
A nickel phosphide catalyst, wherein the catalyst is Ni2P/Al2O3The preparation method of the catalyst of the invention comprises the following steps.
a) Adding soluble salt containing Ni and soluble salt containing metal element A (one or two of Al, Fe and Ce and + 3-valent metal) into deionized water according to a certain molar ratio (1:10-10:1), then adding a certain amount of ammonium fluoride (0.1-0.5 mol/L) and urea (0.25-1.25 mol/L), stirring and dissolving to form clear solution, putting into a polytetrafluoroethylene kettle, setting the temperature and the time, and reacting.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature and the time, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, and then placing the precursor in a muffle furnace to set the temperature and time for roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under the atmosphere of (A), the set temperature,Time and temperature rising rate, and carrying out reduction reaction to obtain the corresponding chimera of the metal or the metal oxide.
e) Calculating and weighing a certain amount of red phosphorus simple substance of the metal chimera obtained in the step d) according to a certain molar ratio, uniformly grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar, and then placing the mixture in a H2And N2In the atmosphere of (2), the temperature, time and temperature rise rate are set, and the second reduction reaction is carried out. Obtaining the corresponding nickel phosphide catalyst with the hydrotalcite structure.
a) The soluble metal salt can be nitrate, citrate, chloride, sulfate, or oxalate; the sum of the molar amount of the + 2-valent metal salt and the molar concentration of the + 3-valent metal salt is 0.025-0.075 mol/L, the molar concentration of ammonium fluoride is 0.1-0.5 mol/L, and the molar concentration of urea is 0.25-1.25 mol/L; a) the temperature of the hydrothermal reaction is 110 ℃, and the time is 20 h; b) the temperature of the medium drying is 60 ℃, and the time is 12 h; c) the roasting temperature of the medium muffle furnace is 400-600 ℃, and the roasting time is 5 hours. d) In the case of intermediate reduction H2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400-500 ℃, the time is 5h, and the heating rate is 2 ℃/min. e) Ni/P2-3, H in the case of medium reduction2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400-500 ℃, the time is 5h, and the heating rate is 2 ℃/min.
Ni2P-Al2O3The application of the catalyst in the catalytic reaction of the lignin monomer is that the lignin monomer guaiacol, the catalyst and a reaction solvent are mixed and then added into a reaction kettle, and hydrogen is introduced after the reaction kettle is closed to replace the air in the reaction kettle. And then heating to the reaction temperature of 150-.
The reaction solvent is one of cyclohexane, methylcyclohexane, methanol, ethanol and decalin, or the mixture of the solvents in any proportion; the liquid product is alcohol, phenol, cyclane or ether compound.
The concentration of guaiacol as a reaction raw material in the reaction solvent is 0.05 to 0.15mol/l, and the mass ratio of guaiacol to the catalyst is (1:1) to (20:1), preferably (1:1) to (10: 1).
Introducing gas at the room temperature of 20-25 ℃ under the pressure of 2-6MPa, then heating up for reaction, and stirring at the speed of 1000r/min in the whole process; preferably raising the temperature to 150 ℃ and 300 ℃, stirring the mixture for reaction for 1 to 5 hours, naturally cooling the mixture to room temperature of 20 to 25 ℃ after the reaction is finished, and reducing the pressure to normal pressure.
Mixing Ni2P/Al2O3The catalyst is applied to the method for preparing organic chemicals from guaiacol, and after the reaction is finished, the filtrate is qualitatively and quantitatively analyzed by gas chromatography.
The invention has the following remarkable advantages:
1. the catalyst prepared by the invention is Ni2P is an active center, the preparation method is simple, and the price of the used raw materials is low.
2. The reaction solvent is a common organic solvent, is environment-friendly and pollution-free, and does not use any inorganic acid or alkali in the reaction process, so that the problem of environmental pollution in the biomass processing technology is avoided.
3. The catalyst used in the invention has the characteristics of stronger low-temperature activity ratio, obvious comparison with other catalysts and greatly reduced resource consumption.
4. The conversion rate of the lignin monomer guaiacol is high and can reach 100%, and the product has cycloalkane as the main product, and the yield is more than 80%. The catalyst has strong selectivity to products, and the main product has wide industrial application and good industrial application prospect.
Drawings
FIG. 1 is an XRD pattern of hydrotalcite precursors of the present invention (examples 1-5) with different Ni/Al ratios;
FIG. 2 shows Ni of different Ni/Al ratios according to the present invention2P-Al2O3XRD patterns of (examples 1-5);
FIG. 3 is the XRD patterns of catalysts of the present invention (examples 1, 5, 6) with different amounts of added P;
FIG. 4a is a 10um SEM image of hydrotalcite from example 3 with a 4:1 Ni/Al ratio; (example 3);
FIG. 4b is a 2um SEM of hydrotalcite from example 3 with a 4:1 Ni/Al ratio; (example 3);
FIG. 4c is a 20um SEM of hydrotalcite from example 4 with a 6:1 Ni/Al ratio; (example 4);
FIG. 4d is a 2um SEM of hydrotalcite from example 4 with a 6:1 Ni/Al ratio. (example 4).
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Ni2P-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01969mol)、Al(NO3)3·9H2Adding O (0.00281mol) into 300ml of deionized water, then adding 0.15mol of ammonium fluoride and 0.06mol of urea, stirring and dissolving to form a clear solution, putting the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 100 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace to set the temperature at 400 ℃ for 5 hours, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the ratio of Ni/P to 2:1, grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar uniformly, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 2
Ni2P-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01125mol)、Al(NO3)3·9H2Adding O (0.01125mol) into 300ml of deionized water, then adding 0.15mol of ammonium fluoride and 0.075mol of urea, stirring and dissolving to form a clear solution, filling the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 150 ℃ for 15 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 5 hours at a set temperature of 400 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation of Ni/P2: 1, uniformly grinding the red phosphorus simple substance and the metal chimera in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 3
Ni2P-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.018mol)、Al(NO3)3·9H2O (0.0045mol) is added into 300ml deionized water, then 0.003mol of ammonium fluoride and 0.375mol of urea are added, stirred and dissolved to form clear solution, and the clear solution is put into a polytetrafluoroethylene kettle, the temperature is set at 130 ℃, the time is 17 hours, and the reaction is carried out.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 5 hours at a set temperature of 500 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation of Ni/P2: 1, uniformly grinding the red phosphorus simple substance and the metal chimera in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the temperature is set to be 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 4
Ni2P-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01928mol)、Al(NO3)3·9H2Adding O (0.00321mol) into 300ml of deionized water, then adding 0.003mol of ammonium fluoride and 0.375mol of urea, stirring to dissolve to form a clear solution, filling the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 11 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 5 hours at a set temperature of 600 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation of Ni/P2: 1, uniformly grinding the red phosphorus simple substance and the metal chimera in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 5
Ni2P-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01992mol)、Al(NO3)3·9H2Adding O (0.00249mol) into 300ml of deionized water, then adding 0.003mol of ammonium fluoride and 0.375mol of urea, stirring to dissolve to form a clear solution, filling the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 100 ℃ for 10 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 3 hours at a set temperature of 600 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation of Ni/P2: 1, uniformly grinding the red phosphorus simple substance and the metal chimera in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 6
Ni12P5-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01125mol)、Al(NO3)3·9H2Adding O (0.01125mol) into 300ml of deionized water, then adding 0.15mol of ammonium fluoride and 0.075mol of urea, stirring and dissolving to form a clear solution, filling the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 80 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 5 hours at a set temperature of 400 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation of Ni/P (3: 1), uniformly grinding the red phosphorus simple substance and the metal chimera in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the temperature is set to be 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 7
Ni-Al2O3The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01125mol)、Al(NO3)3·9H2Adding O (0.01125mol) into 300ml of deionized water, then adding 0.15mol of ammonium fluoride and 0.075mol of urea, stirring and dissolving to form a clear solution, filling the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace for 4 hours at a set temperature of 400 ℃, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 5 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the calculation without adding P, grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar uniformly, and then placing the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 100 ml/L; n is a radical of2The flow rate is 100ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide with the hydrotalcite structure is obtainedA catalyst.
Example 8
Ni2Preparation of P-FeP:
a) mixing Ni (NO)3)2·6H2O(0.01969mol)、Fe(NO3)2·9H2Adding O (0.00281mol) into 300ml of deionized water, then adding 0.15mol of ammonium fluoride and 0.06mol of urea, stirring and dissolving to form a clear solution, putting the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace to set the temperature at 400 ℃ for 5 hours, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 3h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance according to the ratio of Ni/P to 2:1 and Fe/P to 1:1 of the metal chimera obtained in the step d), uniformly grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 3h, and the heating rate is 2 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 9
Ni2P-CeO2The preparation of (1):
a) mixing Ni (NO)3)2·6H2O(0.01969mol)、Ce(NO3)2·6H2O (0.00281mol), into 300ml of deionized water, then 0.15mol of ammonium fluoride and 0.06mol of urea are added,stirring and dissolving to form a clear solution, putting the clear solution into a polytetrafluoroethylene kettle, setting the temperature at 110 ℃ for 20 hours, and carrying out reaction.
b) And after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, placing the precipitate in a vacuum drying oven, setting the temperature at 60 ℃ for 12 hours, and drying.
c) Grinding the dried precursor obtained in the step b) in a mortar to enable the precursor to be fine and uniform, then placing the precursor in a muffle furnace to set the temperature at 400 ℃ for 5 hours, and roasting to form the oxide of the corresponding metal.
d) Calcining the metal oxide obtained in c) in H2And N2Under an atmosphere of (H)2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 450 ℃, the time is 5h, and the heating rate is 2 ℃/min, and the reduction reaction is carried out to obtain the corresponding chimera of the metal or the metal oxide.
e) Weighing quantitative red phosphorus simple substance of the metal chimera obtained in the step d) according to the ratio of Ni/P to 2:1, grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortar uniformly, and then putting the mixture in H2And N2Is subjected to a second reduction reaction in an atmosphere of (2), H2Flow rate: 50 ml/L; n is a radical of2The flow rate is 50ml/L, the set temperature is 500 ℃, the time is 5h, and the heating rate is 5 ℃/min, so that the corresponding nickel phosphide catalyst with the hydrotalcite structure is obtained.
Example 10
And (3) carrying out hydrogenation and deoxidation reaction on guaiacol: the catalyst obtained in example 1 was subjected to guaiacol hydrogenolysis reaction in a batch-type high-pressure reactor, the reaction medium was methylcyclohexane, the internal reaction standard was n-dodecane, the concentration of the reaction raw material was 0.125mol/L, the mass ratio of the substrate to the catalyst was 5:1, the initial pressure of hydrogen filling in the reactor at room temperature was 5MPa, the temperature was raised to 300 ℃, the reaction time was 3 hours, and the number of stirring revolutions was 1000 r/min.
After the reaction is finished, cooling to room temperature, taking a liquid product, and carrying out qualitative and quantitative detection by using a gas chromatography-mass spectrometer and a gas chromatograph.
The result was that the guaiacol conversion reached 99.9%, the main product was cyclohexane, and the yield was 94.6%.
Example 11
And (3) carrying out hydrogenation and deoxidation reaction on guaiacol: the catalyst obtained in example 1 was subjected to guaiacol hydrogenolysis reaction in a batch-type high-pressure reactor, the reaction medium was methanol, the internal reaction standard was n-dodecane, the concentration of the reaction raw material was 0.05mol/L, the mass ratio of the substrate to the catalyst was 1:1, the initial pressure of hydrogen filling in the reactor at room temperature was 5MPa, the temperature was raised to 300 ℃, the reaction time was 3 hours, and the number of stirring revolutions was 1000 r/min.
After the reaction is finished, cooling to room temperature, taking a liquid product, and carrying out qualitative and quantitative detection by using a gas chromatography-mass spectrometer and a gas chromatograph.
The result was that the guaiacol conversion reached 99.9%, the main product was cyclohexane, and the yield was 94.6%.
Example 12
And (3) carrying out hydrogenation and deoxidation reaction on guaiacol: the catalyst obtained in example 1 was subjected to guaiacol hydrogenolysis reaction in a batch-type high-pressure reactor, the reaction medium was ethanol, the internal reaction standard was n-dodecane, the concentration of the reaction raw material was 0.15mol/L, the mass ratio of the substrate to the catalyst was 10:1, the initial pressure of hydrogen filling in the reactor at room temperature was 5MPa, the temperature was raised to 300 ℃, the reaction time was 3 hours, and the number of stirring revolutions was 1000 r/min.
After the reaction is finished, cooling to room temperature, taking a liquid product, and carrying out qualitative and quantitative detection by using a gas chromatography-mass spectrometer and a gas chromatograph.
The result was that the guaiacol conversion reached 99.9%, the main product was cyclohexane, and the yield was 94.6%.
Example 13
Guaiacol hydrodeoxygenation experiments were carried out in a similar manner to example 9, except that the catalyst was changed to the catalysts of examples 5 and 6, and the results are shown in the table (reaction conditions: 300 ℃, 5MPa, 3 h):
as can be seen from the results in the table, different Ni/P ratios have a significant influence on the crystal phase formed by the catalyst and the activity of the catalytic reaction, and when the Ni/P ratio is 2, the yield of cyclohexane as the main product is the highest, and reaches 94.6 percent
Example 14
The guaiacol hydrodeoxygenation reaction experiment changes the experimental temperature condition to 200-300 ℃.
As can be seen from the results in the table, different reaction temperatures have a significant effect on the catalytic activity of the catalyst, and when the temperature is 250 ℃, the activity of the catalyst is still high, and the environmental yield is maintained at a level of 80.6%, thus proving the excellent low-temperature activity of the catalyst.
Claims (10)
1. A hydrotalcite-based nickel phosphide catalyst, the structural formula of which is represented by Ax-Niy-P, wherein x is more than 0 and less than or equal to 10, and y is more than 0 and less than or equal to 10; a is one or two +3 valence metals of Al, Fe and Ce.
2. The method for preparing a hydrotalcite-structured nickel phosphide catalyst according to claim 1, wherein:
a) adding soluble salt containing Ni and soluble salt containing metal element A into deionized water according to a molar ratio, then adding ammonium fluoride and urea, stirring and dissolving to form clear solution, putting the solution into a polytetrafluoroethylene kettle, and carrying out hydrothermal reaction;
b) after the hydrothermal reaction is finished, forming a precipitate with a hydrotalcite-like structure, carrying out suction filtration on the precipitate, and drying the precipitate in a vacuum drying oven;
c) grinding the dried precursor obtained in the step b) in a mortar to make the precursor fine and uniform, and then placing the precursor in a muffle furnace for roasting to form an oxide of a corresponding metal;
d) calcining the metal oxide obtained in c) in H2And N2Carrying out reduction reaction in the atmosphere of (1) to obtain a corresponding metal or metal oxide chimera;
e) taking out and weighing the metal chimera obtained in the step d), calculating and weighing the red phosphorus simple substance according to the molar ratio, and uniformly grinding the red phosphorus simple substance and the red phosphorus simple substance in a mortarThen placing the mixture in H2And N2Carrying out a second reduction reaction in the atmosphere of (3); obtaining the corresponding nickel phosphide catalyst with the hydrotalcite structure.
3. A method according to claim 2, wherein in step a) the soluble metal salt is selected from the group consisting of nitrate, citrate, chloride, sulphate and oxalate; the molar ratio of Ni to the + 3-valent metal is 1: 1-8: 1; the molar quantity of the Ni metal salt and the molar concentration of the + 3-valent metal salt are within 0.025-0.075 mol/L, the molar concentration of the ammonium fluoride is within 0.1-0.5 mol/L, and the molar concentration of the urea is within 0.25-1.25 mol/L.
4. The method as set forth in claim 2, wherein the hydrothermal reaction in step a) is carried out at a temperature of 100 to 150 ℃ for 15 to 20 hours.
5. The method as claimed in claim 2, wherein the drying temperature in step b) is 60-100 ℃ for 10-12 h.
6. The method as set forth in claim 2, wherein the muffle furnace roasting temperature in step c) is 400-600 ℃ for 3-5 hours.
7. The method of claim 2, wherein the H reduced in step d) is2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400-500 ℃, the time is 3-5 h, and the heating rate is 2-5 ℃/min.
8. A method as claimed in claim 2, wherein in step e) Ni/P is 2-3, H is reduced2The flow rate of (A) is 50ml/L to 100ml/L, H2/N2The flow ratio is 1: 1; the reduction temperature is 400-500 ℃, the time is 3-5 h, and the heating rate is 2-5 ℃/min.
9. The use of the hydrotalcite-structured nickel phosphide catalyst of claim 1 in the hydrogenolysis reaction of guaiacol, wherein: the guaiacol hydrogenolysis reaction is carried out in a batch high-pressure reaction kettle, the reaction medium is an organic solvent which does not participate in the reaction, the reaction internal standard substance is n-dodecane, the concentration of the reaction raw material is 0.05-0.15mol/L, the mass ratio of the substrate to the catalyst is 1:1-10:1, the initial pressure of hydrogen filled in the reaction kettle at room temperature is 2-6MPa, the temperature is increased to the reaction temperature of 150 ℃ and 300 ℃, the reaction time is 1-5h, and the stirring revolution is 1000 r/min.
10. Use according to claim 9, characterized in that: the organic solvent is methylcyclohexane, decalin, methanol or ethanol.
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