CN115364856A - Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof Download PDF

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CN115364856A
CN115364856A CN202211144996.4A CN202211144996A CN115364856A CN 115364856 A CN115364856 A CN 115364856A CN 202211144996 A CN202211144996 A CN 202211144996A CN 115364856 A CN115364856 A CN 115364856A
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catalyst
preparing
mannitol
fructose
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CN115364856B (en
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高捷
王浩宇
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Northwestern Polytechnical University
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    • 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
    • B01J23/72—Copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases

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Abstract

The invention belongs to the field of catalysts for preparing mannitol, and particularly relates to a catalyst for preparing mannitol by fructose hydrogenation and a preparation method thereof. The preparation method comprises the following steps: (1) Dissolving an active component precursor and urea in water to obtain a mixed solution, adding alkaline silica sol, stirring and uniformly mixing, and adjusting the pH to 8.5-9.5 by using ammonia water to obtain a precipitate suspension; (2) Transferring the precipitate suspension into a reaction kettle, placing the reaction kettle into a dynamic homogeneous reactor, carrying out hydrothermal reaction at the temperature of 200-250 ℃ for 10-15 h, and carrying out subsequent conventional operation after the reaction to obtain the catalyst. The method of combining ammonia evaporation with hydrothermal can realize accurate adjustment of the surface structure of the catalyst, thereby effectively improving catalytic activity and efficiency, having good selectivity and stability, solving the problem of slow reaction rate of the current copper-based catalyst, and having good application prospect in preparing mannitol by fructose hydrogenation.

Description

Catalyst for preparing mannitol by fructose hydrogenation and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts for preparing mannitol, and particularly relates to a catalyst for preparing mannitol by fructose hydrogenation and a preparation method thereof.
Background
Mannitol is a sugar alcohol substance and is widely applied to the fields of food, medicine, chemical industry and the like at present. Mannitol can be used as sweetener, sobering agent and mouth freshener with low calorific value, and can also be used as dehydrating agent of tissue and vasodilator, and mannitol is also a chemical raw material, and can be used for preparing abietate, explosive, detonator, etc. Particularly, with the increase of fat people and diabetics all over the world, mannitol is used as a sweet substitute with extremely low calorific value, and the demand is increasing continuously, so that the application prospect of mannitol is wider and wider.
In the prior art, the industrial production method of mannitol mainly comprises a kelp extraction method, a microbial fermentation method, a chemical synthesis method and the like. The chemical synthesis method has the advantage of high efficiency and controllability, and the advantages of the chemical synthesis method are more prominent than those of other methods, so that the main production mode of mannitol has been shifted to the chemical synthesis method. The chemical synthesis method is mainly to prepare the mannitol by hydrogenation reaction by using fructose or glucose-fructose mixed solution as a raw material and using a bulk catalyst such as raney nickel and the like. However, the selectivity of mannitol is low with the current process. The results of the Makee et al study show that the VIII group elements such as Ni and the like have 40-50% selectivity in the fructose hydrogenation reaction. Although the traditional noble metal hydrogenation catalyst has higher reaction rate, the selectivity is lower, such as Pt/C and Ru/C catalysts researched by de Wit et al, which have the selectivity of only 45-55%.
The copper catalyst is used as a hydrogenation catalyst, has 65% of selectivity in the preparation reaction of mannitol, and along with the development of research, in a system with the ethanol-water ratio of 3:2, the highest selectivity of the existing copper catalyst can reach 68%. However, the adoption of the Cu catalyst also reveals the problems of low catalytic activity, low product yield and long catalytic reaction time on the basis of improving the selectivity, thereby hindering the industrial application of the catalyst.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a catalyst for preparing mannitol by fructose hydrogenation, so as to solve the problem that the catalyst prepared by the existing process cannot give consideration to catalytic selectivity, product yield and catalytic reaction efficiency in the reaction of preparing mannitol by fructose hydrogenation.
The invention also aims to provide a catalyst for preparing mannitol by fructose hydrogenation, which has high catalytic activity and catalytic selectivity in the reaction of preparing mannitol by fructose hydrogenation, can effectively improve catalytic efficiency and reduce time cost while obtaining higher mannitol yield.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a catalyst for preparing mannitol by fructose hydrogenation comprises the following steps:
(1) Dissolving an active component precursor and urea in water to obtain a mixed solution, adding alkaline silica sol into the mixed solution, uniformly stirring, and adjusting the pH to 8.5-9.5 by using ammonia water to obtain a precipitate suspension; the active component precursor is one of copper nitrate or copper chloride;
(2) Transferring the precipitate suspension obtained in the step (1) into a reaction kettle, then placing the reaction kettle into a dynamic homogeneous reactor, carrying out hydrothermal reaction for 10-15 h at 200-250 ℃, centrifuging, washing, drying, grinding, roasting, and reducing to obtain the catalyst for preparing mannitol by fructose hydrogenation.
The preparation method of the catalyst for preparing mannitol by fructose hydrogenation comprises the steps of blending active components and urea, adding alkaline silica sol, and adjusting pH to form a copper hydroxide precipitation suspension. The invention dissolves urea and active metal precursor in deionized water together, adds alkaline silica sol, improves the adding sequence and precipitation steps of materials to ensure that the active metal on the surface of the catalyst obtained by the subsequent synthesis is more uniformly distributed, further matches with the subsequent one-step synthesis method of combining hydrothermal synthesis and ammonia distillation, adopts a dynamic homogeneous reactor to ensure that the surface metal of the catalyst keeps higher dispersion degree and stability in the hydrothermal reaction process, and finally realizes the comprehensive regulation and control of the surface structure of the catalyst, thereby successfully preparing the supported copper catalyst for preparing mannitol by fructose hydrogenation.
The preparation method of the invention has simple process and is easy to realize industrialization. Tests prove that the catalyst material prepared by the steps has smaller active metal particle size, is uniformly and stably distributed in a bulk phase of a carrier, is used for a reaction for preparing mannitol by fructose hydrogenation, and has the advantages that the hydrogenation selectivity of the catalyst prepared by the steps to mannitol reaches 71-72 percent, the mannitol yield reaches 67 percent in a shorter catalytic reaction time in the same hydrogenation reaction system, the activity and the catalytic efficiency of the catalyst are obviously improved compared with the existing silicon dioxide loaded copper-based catalytic material, and the catalyst material has the double characteristics of high activity and high mannitol selectivity.
In order to further optimize the morphology and size of the catalyst after hydrothermal ammonia distillation reaction and improve the catalytic activity and selectivity of the catalyst, in the step (1), the mass ratio of the active component precursor to the urea to the alkaline silica sol is (0.6-1.2) to (3.8-4.2) to (4.8-5.2), and the more preferable mass ratio is 0.6: 4: 5.
Urea is used in the present invention as a precipitant for precipitation of a copper metal salt and also as a nitrogen source in hydrothermal reactions, and the amount of urea used has a correlation with the reconstitution of the catalyst surface. In order to ensure the structural stability and the catalytic performance of the catalyst, the concentration of urea in the mixed solution in the step (1) is preferably 0.6-0.7 mol/L.
In consideration of ensuring the sufficiency of the hydrothermal ammonia distillation reaction and the morphological uniformity of the product, a certain rotation speed is required to be applied in the hydrothermal process, and preferably, in the step (2), the rotation speed of the homogeneous reactor is 20-40 r/min, and more preferably 30r/min during the hydrothermal reaction.
In the step (2), the rotating speed of the centrifugation is 5000-7000r/min, the centrifugation time is 1-3 min, and the rotating speed is 6000r/min and the centrifugation time is 2min are further preferred.
In the step (2), the drying temperature is 50-70 ℃, and the drying time is 20-30 h; the roasting temperature is 300-400 ℃, and the roasting time is 2-4 h. More preferably, the drying temperature is 60 ℃, and the drying time is 24h; the roasting temperature is 350 ℃, and the roasting time is 3h.
After grinding and roasting, introducing hydrogen into a tubular furnace for reduction, preferably, the reduction specifically comprises: to 10% of H 2 Heating to 220-240 ℃ at the speed of 8-12 ℃/min under the Ar atmosphereReducing for 1.5-2.5 h. Further preferably, 10% H 2 The flow rate of/Ar was 60mL/min.
The technical scheme adopted by the catalyst for preparing the mannitol by hydrogenating the fructose is as follows:
the catalyst for preparing mannitol by hydrogenating fructose is prepared by the preparation method.
In the catalyst prepared by the invention, metal nanoclusters of about 3nm are uniformly dispersed on the surface of a carrier of 20-30nm, and active component metal is in the SiO (silicon dioxide) carrier 2 The catalyst has high dispersity and uniform particle size, belongs to a nano-scale catalyst, and nanoclusters with smaller sizes ensure the selectivity of mannitol, further improve the reaction activity of fructose hydrogenation and improve the catalytic efficiency. Experiments prove that compared with the fructose hydrogenation copper-based catalyst in the prior art, the catalyst provided by the invention has the advantages that the activity is obviously improved, the selectivity and the stability are good, and the industrial application prospect in the preparation of mannitol by fructose hydrogenation is good.
Drawings
FIG. 1 is a transmission electron microscope (STEM) image of a catalyst prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the catalysts prepared in example 1 of the present invention and comparative examples 1 and 2;
FIG. 3 is a graph of Temperature Programmed Reduction (TPR) of the catalysts prepared in example 1 of the present invention and comparative examples 1 and 2.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments. In the following examples, the materials are all conventional commercial products unless otherwise specified, wherein the basic silica sol used in the following examples is a standard Jn-30 silica sol having a pH of 8.0 to 9.0 and SiO 2 Is about 30%.
Example 1
The preparation process of the catalyst for preparing mannitol by fructose hydrogenation comprises the following steps:
(1) 0.6g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 And dissolving O and 4g of urea in 100mL of pure water by adopting a magnetic stirrer, adding 5g of alkaline silica sol, placing the mixture in an oil bath kettle at the temperature of 80 ℃, stirring for 30min, and then adjusting the pH to 9 by using ammonia water to obtain a dark blue precipitate suspension.
(2) Transferring all the precipitate suspension obtained in the step (1) into a 100mL hydrothermal kettle, transferring the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12h at 225 ℃, and setting the rotating speed of the homogeneous reactor to be 30r/min; after hydrothermal, cooling the product to room temperature in air, centrifuging for 2min at 6000r/min by adopting a centrifuge, pouring out the supernatant, washing by using pure water, and repeating the centrifuging and washing operations for 5 times to obtain a precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; subsequent 10% H in a tube furnace using 60mL/min 2 In the atmosphere of/Ar, the temperature is raised to 230 ℃ at the speed of 10 ℃/min, and the reduction is carried out for 2h, thus obtaining the catalyst for preparing mannitol by fructose hydrogenation in the embodiment 1.
Example 2
The preparation process of the catalyst for preparing mannitol by fructose hydrogenation according to the embodiment comprises the following steps:
(1) 0.9g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 And dissolving O and 4g of urea in 100mL of pure water by adopting a magnetic stirrer, adding 5g of alkaline silica sol, placing the mixture in an oil bath kettle at the temperature of 80 ℃, stirring for 30min, and then adjusting the pH to 9 by using ammonia water to obtain a dark blue precipitate suspension.
(2) Transferring all the precipitate suspension obtained in the step (1) into a 100mL hydrothermal kettle, transferring the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12h at 225 ℃, and setting the rotating speed of the homogeneous reactor to be 30r/min; after hydrothermal, cooling the product to room temperature in air, centrifuging for 2min at 6000r/min by adopting a centrifuge, pouring out the supernatant, washing by using pure water, and repeating the centrifuging and washing operations for 5 times to obtain a precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; then in a tube furnaceUsing 10% of 60mL/min 2 And in an/Ar atmosphere, heating to 230 ℃ at the temperature of 10 ℃/min, and reducing for 2h to obtain the catalyst for preparing mannitol by fructose hydrogenation in the embodiment 2.
Example 3
The preparation process of the catalyst for preparing mannitol by fructose hydrogenation according to the embodiment comprises the following steps:
(1) Weighing 1.2g Cu (NO) 3 ) 2 ·2.5H 2 And dissolving O and 4g of urea in 100mL of pure water by adopting a magnetic stirrer, adding 5g of alkaline silica sol, placing the mixture in an oil bath kettle at the temperature of 80 ℃, stirring for 30min, and then adjusting the pH value to 9 by using ammonia water to obtain a dark blue precipitate suspension.
(2) Transferring all the precipitate suspension obtained in the step (1) into a 100mL hydrothermal kettle, transferring the hydrothermal kettle into a homogeneous reactor, carrying out hydrothermal reaction for 12h at 225 ℃, and setting the rotating speed of the homogeneous reactor to be 30r/min; after hydrothermal, cooling the product to room temperature in air, centrifuging for 2min at 6000r/min by adopting a centrifuge, pouring out the supernatant, washing by using pure water, and repeating the centrifuging and washing operations for 5 times to obtain a precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; subsequent 10% H in a tube furnace using 60mL/min 2 In the atmosphere of/Ar, the temperature is raised to 230 ℃ at the speed of 10 ℃/min, and the catalyst for preparing mannitol by fructose hydrogenation of the example 3 is obtained after 2h of reduction.
Comparative example 1
The catalyst of the comparative example is prepared by adopting an ammonia distillation method in the prior art, and the preparation process comprises the following steps:
(1) 0.6g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 And dissolving O and 4g of urea in 100mL of pure water by adopting a magnetic stirrer, adding 5g of alkaline silica sol, placing the mixture in an oil bath kettle at the temperature of 80 ℃, stirring for 30min, and then adjusting the pH value to 9 by using ammonia water to obtain a dark blue precipitate suspension.
(2) Aging the precipitate suspension obtained in step (1) at 80 deg.C for 4 hr, centrifuging at 6000r/min for 2min, pouring out supernatant, washing with pure water, and repeatingCentrifuging and washing for 5 times to obtain precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; subsequent 10% H in a tube furnace using 60mL/min 2 Heating to 230 ℃ at the speed of 10 ℃/min in the atmosphere of/Ar, and reducing for 2h to obtain the catalyst of the comparative example 1.
Comparative example 2
The catalyst of the comparative example is prepared by a deposition precipitation method in the prior art, and comprises the following specific steps:
(1) 0.6g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 Dissolving O in 50mL of pure water, carrying out oil bath at 80 ℃ to form a copper salt solution, adding 5g of alkaline silica sol into the copper salt solution to form a suspension,
(2) Using 1mol/L of K 2 CO 3 Titrating to the suspension to make the pH value reach 7.2-7.4, aging the obtained suspension at 70 ℃ for 5h, centrifuging at 6000r/min for 2min by adopting a centrifuge, pouring out the supernatant, washing by using pure water, and repeating the centrifuging and washing operations for 5 times to obtain a precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; subsequent 10% H in a tube furnace using 60mL/min 2 Heating to 230 ℃ at the speed of 10 ℃/min in the atmosphere of/Ar, and reducing for 2h to obtain the catalyst of the comparative example 2.
Comparative example 3
The catalyst of the comparative example is prepared by a coprecipitation method in the prior art, and the specific preparation process is as follows:
(1) Weighing 16.8g of sodium hydroxide, adding the sodium hydroxide into 70mL of pure water, and uniformly stirring the mixture by using a glass rod to obtain 6mol/L sodium hydroxide solution; 1.51g of cerous nitrate hexahydrate and 0.06g of Cu (NO) were weighed 3 ) 2 ·2.5H 2 Dissolving O in 10mL of water to obtain a precursor nitrate solution; dropwise adding the precursor nitrate solution into the vigorously stirred sodium hydroxide solution, continuously stirring for 30min after all the dropwise adding is finished, and precipitating to obtain a suspension;
(2) Mixing the suspension obtained in the step (1)Partially transferring the mixture into a hydrothermal kettle, and carrying out hydrothermal reaction in a homogeneous reactor at 120 ℃ for 24 hours; centrifuging the solution for 2min at 2800r/min after hydrothermal treatment, pouring out the supernatant, washing with pure water, and centrifuging and washing for 3 times continuously to obtain a precipitate; drying the obtained precipitate in an oven at 70 ℃ for 12h; after grinding, the temperature is raised from room temperature to 400 ℃ at the temperature raising rate of 5 ℃/min in the air atmosphere, and the monoatomic copper catalyst (Cu/CeO) of the comparative example 3 can be obtained after roasting for 2h 2 )。
Comparative example 4
The catalyst of the comparative example was prepared by the impregnation method of the prior art, and the specific preparation process was as follows:
(1) 0.6g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 Adding 2mL of water into O for dissolving, dropwise adding the O into 2g of carbon nano tube, then placing the carbon nano tube in the air for standing, and stirring once every 20min until the catalyst is completely dried to obtain catalyst powder;
(2) Heating the obtained powder from room temperature to 350 deg.C at a heating rate of 5 deg.C/min in air atmosphere, calcining for 3h, and then using 10% H of 60mL/min in a tube furnace 2 And (3) heating to 230 ℃ at the temperature of 10 ℃/min under the Ar atmosphere, and reducing for 2h to obtain the catalyst of the comparative example 4, wherein the catalyst is named as Cu/CNT.
Comparative example 5
The catalyst of the comparative example is prepared by adopting a water bath ammonia distillation method in the prior art, and the preparation process comprises the following steps:
(1) 0.6g of Cu (NO) was weighed 3 ) 2 ·2.5H 2 Dissolving O in 100mL of pure water, and continuously stirring until the O is completely dissolved to form a copper salt solution;
(2) Adding 4g of urea into the copper salt solution obtained in the step (1) to obtain a dark blue precipitate suspension, uniformly stirring by using a magnetic stirrer, then adjusting the pH value of the suspension to 11 by dropwise adding ammonia water, and finally adding 5g of alkaline silica sol and uniformly stirring;
(3) Placing the mixed solution added with the alkaline silica sol in the step (2) in a water bath at 80 ℃, stirring and reacting for 12h, cooling the product to room temperature after the reaction, then adopting a centrifuge to centrifuge for 2min at 6000r/min, pouring off the supernatant, washing with pure water,repeating the operations of centrifuging and washing for 5 times to obtain precipitate; then drying the precipitate in an oven at 60 ℃ for 24 hours; drying and grinding, heating to 350 ℃ from room temperature at a heating rate of 5 ℃/min in an air atmosphere after grinding, and roasting for 3h; subsequent 10% H in a tube furnace using 60mL/min 2 Heating to 230 ℃ at the speed of 10 ℃/min in the atmosphere of/Ar, and reducing for 2h to obtain the catalyst of the comparative example 5.
Test example 1 characterization of physicochemical Properties
This test example transmission electron microscopy (STEM) analysis of fine structure imaging was carried out on the catalyst obtained in example 1 of the present invention, and the STEM spectrum obtained is shown in FIG. 1. Further, the catalyst samples of example 1 and comparative examples 1 to 2 were subjected to X-ray diffraction analysis (XRD) and temperature-programmed reduction (TPR) analysis, as shown in fig. 2 and 3.
Fig. 1 is a microscopic image of the catalyst of example 1 under different times, and it can be seen that the dispersion degree of the catalyst is relatively uniform. The 2nm scale plot in FIG. 1 shows clear lattice fringes, where the lattice spacing of the Cu (111) planes is about 0.21nm 2 The lattice spacing of the O (211) crystal plane is about 0.17nm. In addition, the invention also finds that the material surface is distributed more uniformly through the result of the spherical aberration transmission electron microscope, and no obvious metal nano-particle agglomeration exists.
As can be seen from fig. 2, characteristic peaks appear at 2 θ =42.4 °, 52.6 ° and 61.5 ° in all the samples, and correspond to Cu respectively 2 The (200), (211) and (220) crystal planes of O; and the adjacent 2 theta =43.3 ° and 50.5 ° show characteristic peaks corresponding to the (111) and (200) crystal planes of the Cu pair, respectively. XRD diffraction results show that the surface of the catalyst does not expose strong crystal face signals, and the surface metal is dispersed uniformly.
As shown in FIG. 3, the Temperature Programmed Reduction (TPR) results of the catalyst revealed that the catalyst sample of example 1 was not completely reduced at about 230 ℃ and still had a part of Cu after 230 ℃ reduction 2 The presence of an O reduction peak, and a little Cu was presumed 2 The synergistic effect of the O phase and the nanocu clusters is the main reason for improving the catalyst activity.
Test example 2 characterization of catalytic Properties
The catalytic performance of the catalysts prepared in examples 1 to 3 and comparative examples 1 to 5 was characterized. The specific operation process is as follows:
weighing 15mL of a solvent (9 mL of ethanol and 6mL of water) by using a measuring cylinder, adding the solvent, the fructose and the catalyst into a 50mL high-pressure reaction kettle according to a mass ratio of 75; introducing hydrogen into the reaction kettle to ensure that the pressure of the hydrogen in the kettle reaches 4MPa, stirring, and raising the temperature to 100 ℃ for 3 hours; after the reaction is finished, taking out the product and the catalyst in the reaction kettle when the temperature of the reaction kettle is cooled to 30 ℃. And (3) carrying out suction filtration and drying, fully cleaning by using a mixture of ethanol and water, and carrying out crystallization separation to obtain the catalyst after the reaction is finished. And analyzing the product of the liquid obtained by filtering in a high performance liquid chromatography, and evaluating the performance of the catalyst according to the experimental result. The results are shown in Table 1.
TABLE 1 influence of the catalysts obtained in the examples and comparative examples on the catalytic performance of hydrogenation of fructose to mannitol
Figure BDA0003854884420000071
The catalyst comprises a silica-supported copper-based catalytic material prepared by an ammonia evaporation method, a silicon dioxide-supported copper-based catalytic material prepared by a deposition precipitation method, a monatomic copper catalyst material prepared by a coprecipitation method, a carbon nanotube/copper-based material prepared by an impregnation method, and a water bath ammonia evaporation method, wherein the comparative example 1 is the silica-supported copper-based catalytic material prepared by the ammonia evaporation method, the comparative example 2 is the silica-supported copper-based catalytic material prepared by the deposition precipitation method, the comparative example 3 is the monatomic copper catalyst material prepared by the coprecipitation method, the comparative example 4 is the carbon nanotube/copper-based material prepared by the impregnation method, and the comparative example 5 is the silica-supported copper-based catalytic material prepared by the water bath ammonia evaporation method.
The results in Table 1 show that the catalyst prepared by the invention has the hydrogenation selectivity of mannitol of 71-72% and the yield of mannitol of 67% in a short catalytic time (3 h) in the reaction of preparing mannitol by catalyzing fructose hydrogenation. Therefore, compared with the existing catalytic materials of comparative examples 1-5, the catalyst material disclosed by the invention has excellent reaction activity while maintaining higher selectivity, is beneficial to improving the catalytic efficiency and reducing the time cost, and has obvious technical advantages, and the yield of reaction products is improved by more than one time within a shorter reaction time.
In conclusion, the catalyst has good application prospect in the aspect of catalyzing fructose hydrogenation to prepare mannitol.

Claims (9)

1. A preparation method of a catalyst for preparing mannitol by fructose hydrogenation is characterized by comprising the following steps:
(1) Dissolving an active component precursor and urea in water to obtain a mixed solution, adding alkaline silica sol into the mixed solution, uniformly stirring, and adjusting the pH to 8.5-9.5 by using ammonia water to obtain a precipitate suspension; the active component precursor is one of copper nitrate or copper chloride;
(2) Transferring the precipitate suspension obtained in the step (1) into a reaction kettle, then placing the reaction kettle into a dynamic homogeneous reactor, carrying out hydrothermal reaction for 10-15 h at 200-250 ℃, centrifuging, washing, drying, grinding, roasting, and reducing to obtain the catalyst for preparing mannitol by fructose hydrogenation.
2. The method for preparing the catalyst for preparing mannitol by hydrogenating fructose according to claim 1, wherein in the step (1), the alkaline silica sol is Jn-30 silica sol.
3. The method for preparing the catalyst for preparing the mannitol by hydrogenating the fructose as claimed in claim 1, wherein in the step (1), the mass ratio of the active component precursor to the urea to the alkaline silica sol is (0.6-1.2) to (3.8-4.2) to (4.8-5.2).
4. The method according to claim 1, wherein in the step (1), the concentration of urea in the mixed solution is 0.6 to 0.7mol/L.
5. The method for preparing a catalyst used in the preparation of mannitol by hydrogenating fructose according to any one of claims 1 to 4, wherein in the step (2), the rotation speed of the homogeneous reactor is 20 to 40r/min during the hydrothermal reaction.
6. The method for preparing the catalyst for preparing mannitol by hydrogenating fructose according to any one of claims 1 to 4, wherein in the step (2), the rotating speed of the centrifugation is 5000 to 7000r/min, and the centrifugation time is 1 to 3min.
7. The method for preparing the catalyst for preparing mannitol by hydrogenating fructose according to any one of claims 1 to 4, wherein in the step (2), the drying temperature is 50-70 ℃, and the drying time is 20-30 h; the roasting temperature is 300-400 ℃, and the roasting time is 2-4 h.
8. The method for preparing the catalyst for preparing mannitol by hydrogenating fructose according to any one of claims 1 to 4, wherein in the step (2), the reduction is specifically: to 10% of H 2 Heating to 220-240 ℃ at the speed of 8-12 ℃/min under Ar atmosphere, and reducing for 1.5-2.5 h.
9. A catalyst for preparing mannitol by hydrogenating fructose, which is prepared by the preparation method of the catalyst for preparing mannitol by hydrogenating fructose according to any one of claims 1 to 8.
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