CN108114748B - Magnetic heteropoly acid catalyst and preparation method thereof - Google Patents
Magnetic heteropoly acid catalyst and preparation method thereof Download PDFInfo
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- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract
The invention relates to a magnetic heteropoly acid catalyst and a preparation method thereof, which comprises the following steps of (1) adding a metal precursor into an organic solvent to prepare a solution A; (2) adding an organic ligand into an organic solvent to prepare a solution B; (3) feeding the solution A and the solution B into a microchannel reactor module I at a certain flow rate to generate MOFs crystal seeds in situ; (4) adding heteropoly acid into water, and stirring to obtain a solution C; adding the magnetic oxide into water, and stirring to obtain a solution D; when the feed liquid in the step (3) enters the module II, feeding the solution C and the solution D into the module II at a certain flow rate; (5) and (4) when the feed liquid in the step (4) enters the module III, feeding the solution B into the module III at a certain flow rate, and finishing a seed crystal induced crystallization reaction under an ultrasonic condition to obtain the magnetic heteropoly acid catalyst. The magnetic heteropolyacid catalyst is prepared by combining a microchannel reactor with an ultrasonic condition, and the heteropolyacid and the magnetic substance have the advantages of dispersibility, short preparation time and high production efficiency.
Description
Technical Field
The invention relates to a heteropoly acid catalyst, in particular to a magnetic heteropoly acid catalyst and a preparation method thereof.
Background
Heteropolyacids are multimetal oxygen cluster compounds composed of a class of transition metals, the structure of which can be regulated and controlled at the molecular or atomic level, and have wide application in the fields of catalysis, electrochemistry, bioscience, material science and the like. Heteropolyacids are an excellent class of homogeneous catalytic materials, yet difficult to separate from the liquid phase reaction medium. Therefore, researchers have been concerned with the heterogenization of heteropoly acids. Because the specific surface area of the heteropoly acid is low, the research on the heteropoly acid packaging carrier has important practical application significance. At present, the commonly used heteropoly acid packaging carrier comprises silicon dioxide, active carbon, silica gel, resin, mesoporous molecular sieve and TiO2And the like.
Metal organic framework Materials (MOFs), also known as metal coordination polymers, refer to crystalline materials formed by connecting inorganic metals or metal clusters and nitrogen-oxygen-containing polydentate organic ligands through coordination bonds, and are organic functionalized porous materials with high specific surface area and adjustable pore sizes. The MOF material can select different organic ligands and metal ions to build pore channels with different sizes and structures according to different sizes of heteropoly acid particles, so that the MOF material is paid more and more attention as an encapsulated heteropoly acid in recent years.
CN103769036 discloses a preparation method of a Keggin-type polytungstate and molecular-based porous material MIL-101 composite material and application of dye adsorption of the composite material, wherein tetramethylammonium hydroxide, terephthalic acid, chromium nitrate, a Keggin-type polytungstate compound and water are mixed according to a certain mass ratio, the mixture is placed into a high-pressure reaction kettle to react for 2-3 days at the temperature of 175-185 ℃, and the mixture is cooled to room temperature and is respectively washed by deionized water and N, N-dimethylformamide to obtain the polytungstate @ MIL-101 composite material. The prepared material can be used for adsorbing cationic organic dye, the adsorption rate of methylene blue in a short time can reach 98%, and the adsorption effect is obviously higher than that of a pure MIL-101 material and higher than the adsorption capacity of activated carbon.
CN103191786 discloses a preparation method of MIL-100(Fe) encapsulated phosphotungstic heteropoly acid catalyst, which comprises the steps of adding raw materials of phosphotungstic heteropoly acid into a certain amount of deionized water according to a certain proportion, then adding a certain amount of iron source, mixing and stirring, then adding a certain amount of organic ligand, mixing and stirring, then adding a certain amount of acid solution, mixing and stirring; then mixing and stirring the mixture at the normal pressure and the temperature of between 80 and 95 ℃ for reaction for 5 to 20 hours; filtering the obtained solid, washing the solid for 10 to 20 hours at the temperature of between 60 and 80 ℃ by using absolute ethyl alcohol, then treating the solid for 10 to 15 hours at the temperature of between 60 and 80 ℃ by using 30 to 60mmol/L ammonium fluoride solution, then fully washing the solid by using deionized water, and finally drying the solid for 5 to 10 hours at the temperature of between 100 and 200 ℃ to obtain the MIL-100(Fe) encapsulated phosphotungstic heteropoly acid catalyst.
The methods for preparing the heteropoly acid catalyst are all batch reaction synthesis methods, have the defects of long reaction time, unstable product performance and the like in the preparation process, and are not beneficial to large-scale industrial production of products.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a magnetic heteropoly acid catalyst and a preparation method thereof. The invention adopts the microchannel reactor to prepare the magnetic heteropoly acid catalyst under the ultrasonic condition, can obtain products with narrow particle size distribution and good dispersity of heteropoly acid and magnetic substances, and can shorten the preparation time and improve the production efficiency.
The preparation method of the magnetic heteropoly acid catalyst comprises the following steps:
(1) adding a metal precursor into an organic solvent, stirring and dissolving to obtain a solution A;
(2) adding an organic ligand into an organic solvent, stirring and dissolving to obtain a solution B;
(3) respectively sending the solution A and the solution B into a micro-channel reactor module I according to a certain flow rate to generate MOFs crystal seeds in situ, and sending a product feed liquid into a micro-channel reactor module II after reacting for a certain time;
(4) adding heteropoly acid into water, and stirring to obtain a solution C; adding the magnetic oxide into water, and stirring to obtain a solution D; when the feed liquid obtained in the step (3) enters the module II, feeding the solution C and the solution D into the module II according to a certain flow rate, and after reacting for a certain time, feeding the product feed liquid into a micro-channel reactor module III;
(5) when the feed liquid obtained in the step (4) enters the module III, feeding the solution B into the module III according to a certain flow velocity, and completing a crystal seed induced crystallization reaction under an ultrasonic condition to obtain a magnetic heteropoly acid catalyst suspension;
(6) and (4) carrying out solid-liquid separation on the magnetic heteropoly acid suspension prepared in the step (5), washing the solid with ethanol, and drying at the temperature of 80-120 ℃ for 8-24 h.
The metal precursor in step (1) of the invention is one or more of sulfate, nitrate, acetate, carbonate, halide or hydrate of copper, iron, zirconium, zinc, magnesium, aluminum, cobalt, chromium, nickel, calcium and titanium, and preferably is ferric chloride. The organic solvent is one or more of water, methanol, ethanol, isopropanol, glycol, isobutanol, glycerol, N-dimethylformamide, N-diethylformamide and N, N-diethylacetamide, preferably water, methanol or ethanol, and more preferably water. The concentration of the metal precursor in the solution A is 0.01-5.0mol/L, preferably 0.1-2.0 mol/L.
The organic ligand in the step (2) is a polydentate organic compound, preferably a bidentate or tridentate carboxylic acid ligand compound and derivatives thereof, and comprises terephthalic acid, isophthalic acid, trimesic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid and the like, preferably trimesic acid; derivatives refer to carboxylic acid ligand compounds in which one or more of the carboxylic acid functional groups are replaced with nitro, hydroxy, methyl, cyano, and the like functional groups. The organic solvent is one or more of methanol, ethanol, isopropanol, glycol, isobutanol, glycerol, N-dimethylformamide, N-diethylformamide and N, N-diethylacetamide, preferably methanol, ethanol or isopropanol, more preferably isopropanol. The concentration of the organic ligand in the solution B is 0.01-10mol/L, preferably 0.1-2.0 mol/L.
The flow rate of the solution A in the step (3) of the present invention is 0.1 to 2000. mu.l/min, preferably 5 to 200. mu.l/min. The flow rate of solution B is 0.1 to 2000. mu.l/min, preferably 5 to 200. mu.l/min. After the solutions A and B enter the microchannel reactor module I, the reaction temperature is 30-80 ℃, preferably 50-70 ℃, the reaction pressure is 0.1-2.0MPa, preferably 0.1-1.0MPa, and the reaction time is 1-600s, preferably 30-180 s.
The heteropoly acid in the step (4) of the invention is one or more of heteropoly acids with Keggin structure and derivatives thereof, preferably phosphotungstic acid, phosphomolybdic acid, tungstosilicic acid, molybdosilicic acid, sodium phosphotungstate, ammonium phosphotungstate, silver phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, silver phosphomolybdate, sodium tungsten silicate, ammonium tungstic silicate, silver tungstic silicate, sodium molybdenum silicate and copper molybdenum silicate, and more preferably phosphotungstic acid. The concentration of the solution C is 0.01-10mol/L, preferably 0.05-0.5 mol/L. The flow rate of solution C is 0.1 to 2000. mu.l/min, preferably 5 to 100. mu.l/min.
The magnetic oxide in the step (4) of the invention is one or more of ferroferric oxide, ferric oxide, chromium dioxide, cobaltosic oxide and the like, and is preferably ferroferric oxide. The concentration of the solution D is 0.01 to 10mol/L, preferably 0.05 to 0.1 mol/L. The flow rate of solution D is 0.1 to 2000. mu.l/min, preferably 5 to 100. mu.l/min.
The flow rate of the product feed liquid containing the MOFs crystal seeds in the step (4) of the invention to be sent into the micro-channel reactor module II is 0.2-2000 mul/min, and preferably 10-400 mul/min. The reaction temperature of the module II in the step (4) is 30-150 ℃, preferably 70-110 ℃, the reaction pressure is 0.1-2.0MPa, preferably 0.1-1.0MPa, and the reaction time is 1-600s, preferably 60-240 s.
The flow rate of the solution B in the step (5) of the present invention is 0.1 to 2000. mu.l/min, preferably 5 to 200. mu.l/min. The reaction temperature of the module III is 80-200 ℃, and preferably 120-180 ℃; the reaction pressure is 0.1-2.0MPa, preferably 0.1-1.0 MPa; the reaction time is from 1 to 600s, preferably from 60 to 300 s.
The frequency of the ultrasonic wave in the step (5) of the invention is 20-100KHz, and the power is 120-800W.
The magnetic heteropoly acid suspension liquid in the step (6) of the invention is subjected to solid-liquid separation by means of high-speed centrifugation or suction filtration and the like.
In step (3) and step (5) of the present invention, an acid is added to the solution B to adjust the pH of the reaction system to 1 to 7, preferably 2 to 4. The acid can be hydrochloric acid, acetic acid, citric acid, hydrofluoric acid, sulfuric acid, preferably hydrochloric acid. The pH value of the reaction system is adjusted to be 2-4 in the processes of in-situ generation of MOFs crystal seeds and seed crystal induction, and the generation and growth of MOFs crystal seeds in the module I and MOFs crystals in the module II are facilitated.
The module I, the module II and the module III of the microchannel reactor are connected in series, and a plurality of reactors connected in series with the module I, the module II and the module III can be connected in parallel according to actual production requirements. The material of the reactor is special glass, ceramics, polytetrafluoroethylene, stainless steel or alloy and the like. The reactor is in the shape of heart, diamond, rectangle, etc. to enhance the mixing of reactant, and has inner diameter of 10-2000 microns. The microchannel reactor module comprises at least two feeding ports and a discharging port, and the number and the positions of the feeding ports can be changed according to reaction requirements.
The magnetic heteropoly acid catalyst of the inventionThe catalyst is prepared by the method of the invention, the proportion of the metal organic framework material in the catalyst is 30-80 wt%, the proportion of the heteropoly acid is 10-45 wt%, the proportion of the magnetic substance is 5-20 wt%, and the specific surface area is 700-1200m2The ratio of medium strong acid/weak acid is 2-12, and the ratio of medium strong acid/strong acid is 2-8.
The magnetic heteropolyacid catalyst can be used as a heterogeneous magnetic catalyst and applied to alkylation, isomerization, esterification, catalytic oxidation and other reactions, particularly to a reaction for preparing and synthesizing 5-hydroxymethylfurfural from glucose.
Compared with the prior art, the method has the following outstanding advantages:
(1) the magnetic heteropoly acid catalyst is prepared by combining the microchannel reactor with the ultrasonic condition, so that a catalyst product with narrow particle size distribution, good dispersity of heteropoly acid and magnetic substances and good reuse effect can be obtained, the preparation time can be shortened, and the utilization rate of heteropoly acid and magnetic substances can be improved. Compared with the preparation method of the similar product, the preparation method has the characteristics of simple preparation process and short period, and is more suitable for industrial batch production.
(2) The microchannel reactor is a reactor consisting of a plurality of microchannel modules, has the characteristics of high mass transfer and high heat transfer, encapsulates heteropoly acid while preparing a metal organic framework material in situ, solves the defect of the traditional method for encapsulating heteropoly acid, and has the advantages of difficult decomposition of heteropoly acid and good encapsulation effect.
(3) The ultrasonic condition is combined with the multi-module micro-channel reactor, so that the ratio of medium strong acid/weak acid and medium strong acid/strong acid can be accurately controlled, and the heteropoly acid catalyst suitable for catalyzing the reaction and distributing acidity can be prepared.
Drawings
FIG. 1 is a schematic structural view of a three-module microchannel reactor used in the method of the present invention;
wherein 1, 2 are the feed inlet of module I, 3 is the discharge gate of module I, 4, 5 are the feed inlet of module II, 6 are the discharge gate of module II, 7, 8 are the feed inlet of module III, 9 are the discharge gate of module III.
FIG. 2 shows an embodiment of the present inventionEXAMPLES 1-5, COMPARATIVE EXAMPLES 1-3 Synthesis of catalysts and MIL-100(Fe) and Fe3O4XRD pattern of (a).
FIG. 3 is an SEM image of a synthesized sample of example 3 of the method of the present invention.
Detailed Description
The present invention is further illustrated by the following examples and comparative examples, but the scope of the present invention is not limited by the examples. The reagents and materials described in the following examples and comparative examples are commercially available unless otherwise specified.
The embodiment of the invention adopts a three-module micro-channel reactor, as shown in figure 1. The specific process comprises the steps of dissolving a metal precursor in an organic solvent to form a solution A, dissolving an organic ligand in the organic solvent to form a solution B, dissolving a heteropoly acid in water to form a solution C, and stirring and mixing a magnetic oxide and water to form a solution D. The solution A and the solution B enter the module I for mixed reaction through the feed inlets 1 and 2 according to a certain flow velocity, feed liquid containing MOFs crystal seeds is formed at a certain temperature and under a certain pressure, the feed liquid flows out of the discharge outlet 3 and enters the module II through the feed inlet 4 according to a certain flow velocity, the feed liquid is mixed and reacted with the solution C and the solution D entering the feed inlet 5, after the reaction is carried out for a certain time at a certain temperature and under a certain pressure, the feed liquid flows out of the discharge outlet 6 and enters the module III through the feed inlet 7 according to a certain flow velocity, the reaction is mixed and reacted with the solution B entering the feed inlet 8, and the crystal seed induced crystallization reaction is completed under. And finally, carrying out solid-liquid separation on the obtained suspension, washing the solid with ethanol, and drying at 80-120 ℃ for 8-24 h.
The microchannel reactor adopted in the embodiment of the invention is a commercially available microchannel reactor, the material of the reactor is stainless steel, the structure is heart-shaped, and the inner diameter of the reactor is 10-2000 microns.
The conveying equipment of the reaction solution in the embodiment of the invention is a high-pressure infusion pump, and adopts a 305SFM01 III model, the pressure range is 0-6000psi, the flow control precision is 0.2%, and the flow rate range is 0.001-5 ml/min.
In the invention, the particle size distribution is obtained by calculating the particle size distribution curve of the particles obtained by the test of a particle size distribution instrument. The heteropolyacid load and the dispersibility are obtained by combined analysis of XRD and BET data; the utilization rate of heteropoly acid: the ratio of the mass difference between the mass of the heteropoly acid in the feeding and the mass of the heteropoly acid in the residual liquid to the mass of the heteropoly acid in the feeding is determined, wherein the mass of the heteropoly acid in the feeding and the mass of the heteropoly acid in the residual liquid are quantitatively analyzed through a chromatogram; the ratio of medium to strong and medium to weak acids was obtained from the NH3-TPD analysis data. The magnetic substance load and the dispersity are obtained through combined analysis of XRD and BET data; utilization ratio of magnetic substance: the ratio of the difference between the amount of the magnetic substance in the feed and the amount of the magnetic substance in the residual liquid to the amount of the magnetic substance in the feed, wherein the amount of the magnetic substance in the feed and the amount of the magnetic substance in the residual liquid are quantitatively analyzed by chromatography.
Example 1
13.52g of ferric trichloride is dissolved in 500ml of water to form a solution A, 10.51g of trimesic acid is dissolved in 500ml of isopropanol to form a solution B, 71.2g of phosphotungstic acid is dissolved in 500ml of water to form a solution C, and 5.8g of ferroferric oxide is mixed with 500ml of water by stirring to form a solution D. Feeding the solution A and the solution B into a micro-channel reactor module I according to the flow rate of 5 mul/min to generate MOFs crystal seeds in situ, wherein the reaction temperature of the module I is 50 ℃, the pressure is 0.1MPa, the retention time is 30s, feed liquid containing the MOFs crystal seeds is generated in the module I, and the feed liquid is fed into a micro-channel reactor module II at the flow rate of 10 mul/min; and (2) feeding the solution C into a micro-channel reactor module II at a flow rate of 5 mul/min, simultaneously feeding the solution D into the module II at a flow rate of 5 mul/min, wherein the reaction temperature is 70 ℃, the pressure is 0.1MPa, the retention time is 60s, feeding the product feed liquid into a module III at a flow rate of 20 mul/min, and feeding the solution B into the module III at a flow rate of 5 mul/min, wherein the reaction temperature of the module III is 120 ℃, the pressure is 0.1MPa, the retention time is 60s, the frequency of ultrasonic waves is 20KHz, and the power is 120W, so as to prepare the magnetic heteropoly acid catalyst suspension. And (3) carrying out solid-liquid separation on the obtained product liquid, washing the solid with ethanol, and drying at 100 ℃ for 24h to obtain the magnetic heteropoly acid catalyst.
XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 23wt%, the magnetic substance content is 15wt%, and the specific surface area is 815m2In/g, ofThe ratio of strong acid/weak acid is 2.3, the ratio of medium strong acid/strong acid is 2.2, the particle size distribution of 0.3-0.5 μm is 68%, the utilization rate of heteropoly acid is 75%, and the utilization rate of magnetic substance is 80%.
Example 2
135.29g of ferric chloride is dissolved in 500ml of water to form a solution A, 210.24g of trimesic acid is dissolved in 500ml of isopropanol to form a solution B, 712g of phosphotungstic acid is dissolved in 500ml of water to form a solution C, and 11.57g of ferroferric oxide is mixed with 500ml of water by stirring to form a solution D. Feeding the solution A and the solution B into a micro-channel reactor module I according to the flow rate of 200 mul/min to generate MOFs crystal seeds in situ, wherein the reaction temperature of the module I is 70 ℃, the pressure is 1.0MPa, the retention time is 180s, feed liquid containing the MOFs crystal seeds is generated in the module I, and the feed liquid is fed into a micro-channel reactor module II at the flow rate of 400 mul/min; and (2) feeding the solution C into a micro-channel reactor module II at the flow rate of 100 mul/min, simultaneously feeding the solution D into the module II at the flow rate of 100 mul/min, wherein the reaction temperature is 110 ℃, the pressure is 1.0MPa, the retention time is 240s, the product feed liquid is fed into a module III at the flow rate of 400 mul/min, and feeding the solution B into the module III at the flow rate of 200 mul/min, wherein the reaction temperature of the module III is 80 ℃, the pressure is 1.0MPa, the retention time is 300s, the frequency of ultrasonic waves is 100KHz, and the power is 800W, so as to prepare the magnetic heteropoly acid catalyst suspension. And (3) carrying out solid-liquid separation on the obtained product liquid, washing the solid with ethanol, and drying at 100 ℃ for 24h to obtain the magnetic heteropoly acid catalyst.
XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 16wt%, the magnetic substance content is 10wt%, and the specific surface area is 824m2The medium-strong acid/weak acid ratio is 2.0, the medium-strong acid/strong acid ratio is 4.4, the particle size distribution of 2-3 μm is 72%, the heteropoly acid utilization rate is 80%, and the magnetic utilization rate is 83%.
Example 3
48.13g of ferric chloride is dissolved in 500ml of water to form a solution A, 100.34g of trimesic acid is dissolved in 500ml of isopropanol to form a solution B, 189.5g of phosphotungstic acid is dissolved in 500ml of water to form a solution C, and 8.9g of ferroferric oxide is mixed with 500ml of water by stirring to form a solution D. Feeding the solution A and the solution B into a micro-channel reactor module I according to the flow rate of 100 mul/min to generate MOFs crystal seeds in situ, wherein the reaction temperature of the module I is 60 ℃, the pressure is 0.5MPa, the retention time is 120s, feed liquid containing the MOFs crystal seeds is generated in the module I, and the feed liquid is fed into a micro-channel reactor module II at the flow rate of 200 mul/min; and (2) feeding the solution C into a micro-channel reactor module II at the flow rate of 50 mul/min, feeding the solution D into the module II at the flow rate of 50 mul/min, feeding the solution D into a module III at the reaction temperature of 100 ℃, the pressure of 0.5MPa and the residence time of 120s, feeding the product feed liquid into the module III at the flow rate of 300 mul/min, and feeding the solution B into the module III at the flow rate of 100 mul/min, wherein the reaction temperature of the module III is 160 ℃, the pressure of 0.5MPa, the residence time of 200s, the frequency of ultrasonic waves is 80KHz, and the power of the ultrasonic waves is 500W, so as to prepare the magnetic heteropoly acid catalyst suspension. And (3) carrying out solid-liquid separation on the obtained product liquid, washing the solid with ethanol, and drying at 100 ℃ for 24h to obtain the magnetic heteropoly acid catalyst.
XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 45wt%, the magnetic substance content is 19wt%, and the specific surface area is 1135m2The medium-strong acid/weak acid ratio is 10.0, the medium-strong acid/strong acid ratio is 6.6, the particle size distribution of 1.0-1.5 mu m is 90%, the heteropoly acid utilization rate is 92%, and the magnetic utilization rate is 90%.
Example 4
The processing flow and the operating conditions were the same as in example 1. The difference lies in that: adding nitric acid into the solution B to adjust the pH value of the reaction system to 2.5. After the reaction is finished, collecting the product liquid, centrifuging, washing with ethanol, and drying at 100 ℃ for 24 h. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 25wt%, the magnetic substance content is 16wt%, and the specific surface area is 975m2The medium-strong acid/weak acid ratio is 5.1, the medium-strong acid/strong acid ratio is 7.6, the particle size distribution of 0.3-0.5 mu m is 80%, the utilization rate of heteropoly acid is 83%, and the utilization rate of magnetic substance is 85%.
Example 5
The processing flow and the operating conditions were the same as in example 1. The difference lies in that: adding into the solution BAdding citric acid to adjust the pH value of the reaction system to 4. After the reaction is finished, collecting the product liquid, centrifuging, washing with ethanol, and drying at 100 ℃ for 24 h. XRD shows that the sample is a magnetic metal organic framework material encapsulated heteropoly acid catalyst, wherein in the catalyst, the heteropoly acid loading capacity is 27wt%, the magnetic substance content is 17wt%, and the specific surface area is 927m2The medium-strong acid/weak acid ratio is 2.5, the medium-strong acid/strong acid ratio is 5.8, the particle size distribution of 0.3-0.5 μm is 75%, the heteropoly acid utilization rate is 78%, and the magnetic utilization rate is 82%.
Example 6
The processing flow and the operating conditions were the same as in example 1. The difference lies in that: the metal precursor in the solution A is copper nitrate, and the organic solvent is ethanol; the organic ligand in the solution B is terephthalic acid, and the organic solvent is ethanol. After the reaction is finished, collecting the product liquid, centrifuging, washing with ethanol, and drying at 100 ℃ for 24 h. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 20wt%, the magnetic substance content is 10wt%, and the specific surface area is 785m2The medium-strong acid/weak acid ratio is 2.8, the medium-strong acid/strong acid ratio is 5.6, the particle size distribution of 0.3-0.5 μm is 60%, the heteropoly acid utilization rate is 65%, and the magnetic utilization rate is 70%.
Example 7
The processing flow and the operating conditions were the same as in example 1. The difference lies in that: the heteropoly acid in the solution C is phosphomolybdic acid. After the reaction is finished, collecting the product liquid, centrifuging, washing with ethanol, and drying at 100 ℃ for 24 h. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 15wt%, the magnetic substance content is 12wt%, and the specific surface area is 750m2The medium-strong acid/weak acid ratio is 4.1, the medium-strong acid/strong acid ratio is 6.8, the particle size distribution of 0.3-0.5 μm is 57%, the heteropoly acid utilization rate is 60%, and the magnetic utilization rate is 75%.
Example 8
The processing flow and the operating conditions were the same as in example 1. The difference lies in that: the magnetic substance in the solution D is cobaltosic oxide. After the reaction is finished, collecting the product liquid, centrifuging,washed with ethanol and dried at 100 ℃ for 24 h. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 18wt%, the magnetic substance content is 14wt%, and the specific surface area is 730m2The medium acid/weak acid ratio is 3.5, the medium acid/strong acid ratio is 8.9, the particle size distribution of 1.0-1.5 μm is 62%, the heteropoly acid utilization rate is 63%, and the magnetic utilization rate is 68%.
Comparative example 1
The process flow and the operating conditions were the same as in example 3. The difference lies in that: the reaction conditions in the module I, the module II and the module III of the microchannel reactor are the same, the reaction temperature is 160 ℃, and the pressure is 1.0 MPa. After the reaction is finished, carrying out solid-liquid separation, washing a filter cake by using ethanol, and drying for 24 hours at the temperature of 100 ℃. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 12wt%, the magnetic substance content is 9wt%, and the specific surface area is 635m2The medium acid/weak acid ratio is 2.9, the medium acid/strong acid ratio is 3.1, the particle size distribution of 1.0-1.5 μm is 55%, the heteropoly acid utilization rate is 58%, and the magnetic utilization rate is 61%.
Comparative example 2
The process flow and the operating conditions were the same as in example 3. The difference lies in that: the reaction conditions in the module I, the module II and the module III of the microchannel reactor are the same, the reaction temperature is 60 ℃, and the pressure is 0.5 MPa. After the reaction is finished, carrying out solid-liquid separation, washing a filter cake by using ethanol, and drying for 24 hours at the temperature of 100 ℃. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 11wt%, the magnetic substance content is 8wt%, and the specific surface area is 621m2The medium-strong acid/weak acid ratio is 2.6, the medium-strong acid/strong acid ratio is 1.7, the particle size distribution of 1.0-1.5 mu m is 53%, the heteropoly acid utilization rate is 55%, and the magnetic utilization rate is 57%.
Comparative example 3
The process flow and the operating conditions were the same as in example 3. The difference lies in that: the microchannel reactor module III has no ultrasonic reaction conditions. After the reaction is finished, solid-liquid separation is carried out, filter cakes are washed by ethanol and dried at 100 DEG CAnd (5) 24 h. XRD shows that the sample is a heteropolyacid catalyst packaged by a magnetic metal organic framework material, wherein in the catalyst, the heteropolyacid loading amount is 10wt%, the magnetic substance content is 5wt%, and the specific surface area is 416m2The medium-strong acid/weak acid ratio is 1.6, the medium-strong acid/strong acid ratio is 2.4, the particle size distribution of 1.0-1.5 mu m is 48%, the heteropoly acid utilization rate is 47%, and the magnetic utilization rate is 45%.
The catalysts prepared in the above examples 1 to 3 and comparative examples 1 to 3 were used for the synthesis of 5-hydroxymethylfurfural in the production of glucose.
TABLE 1 Effect of Using catalysts of examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 1, the catalyst prepared in the embodiment of the invention has high conversion rate and good repeated use effect when used in the reaction of preparing 5-hydroxymethylfurfural from glucose.
Claims (14)
1. A preparation method of a magnetic heteropoly acid catalyst is characterized by comprising the following steps:
(1) adding the metal precursor into an organic solvent or/and water, stirring and dissolving to prepare a solution A;
(2) adding an organic ligand into an organic solvent, stirring and dissolving to obtain a solution B;
(3) respectively sending the solution A and the solution B into a micro-channel reactor module I according to a certain flow rate to generate MOFs crystal seeds in situ, wherein the reaction temperature is 30-80 ℃, the reaction pressure is 0.1-2.0MPa, and sending the product liquid into a micro-channel reactor module II after reacting for a certain time;
(4) adding heteropoly acid into water, and stirring to obtain a solution C; adding the magnetic oxide into water, and stirring to obtain a solution D; when the feed liquid obtained in the step (3) enters the module II, feeding the solution C and the solution D into the module II according to a certain flow rate, wherein the reaction temperature is 30-150 ℃, the reaction pressure is 0.1-2.0MPa, and feeding the product feed liquid into the microchannel reactor module III after reacting for a certain time;
(5) when the feed liquid obtained in the step (4) enters the module III, feeding the solution B into the module III according to a certain flow rate, and finishing a seed crystal induced crystallization reaction under an ultrasonic condition, wherein the reaction temperature is 80-200 ℃, the reaction pressure is 0.1-2.0MPa, the ultrasonic frequency is 20-100KHz, and the power is 120-800W, so as to prepare a magnetic heteropoly acid catalyst suspension;
(6) and (4) carrying out solid-liquid separation on the magnetic heteropoly acid suspension prepared in the step (5), washing the solid with ethanol, and drying at the temperature of 80-120 ℃ for 8-24 h.
2. The method of claim 1, wherein: the metal precursor in the step (1) is one or more of sulfate, nitrate, acetate, carbonate, halide or hydrate of copper, iron, zirconium, zinc, magnesium, aluminum, cobalt, chromium, nickel, calcium and titanium; the organic solvent is one or more of methanol, ethanol, isopropanol, glycol, isobutanol, glycerol, N-dimethylformamide, N-diethylformamide and N, N-diethylacetamide; the concentration of the metal precursor in the solution A is 0.01-5.0 mol/L.
3. The method according to claim 1 or 2, characterized in that: the metal precursor in the step (1) is ferric chloride, and the concentration of the metal precursor in the solution A is 0.1-2.0 mol/L.
4. The method of claim 1, wherein: the organic ligand in the step (2) is a bidentate or tridentate carboxylic acid ligand compound and a derivative thereof, the carboxylic acid ligand compound is terephthalic acid, isophthalic acid, trimesic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid or 2, 6-naphthalenedicarboxylic acid, and the derivative refers to that one or more carboxylic acid functional groups in the carboxylic acid ligand compound are substituted by nitro groups, hydroxyl groups, methyl groups or cyano group functional groups; the organic solvent is one or more of methanol, ethanol, isopropanol, glycol, isobutanol, glycerol, N-dimethylformamide, N-diethylformamide and N, N-diethylacetamide; the concentration of the organic ligand in the solution B is 0.01-10 mol/L.
5. The method according to claim 1 or 4, characterized in that: the organic ligand in the step (2) is trimesic acid, the organic solvent is isopropanol, and the concentration of the organic ligand in the solution B is 0.1-2.0 mol/L.
6. The method of claim 1, wherein: the flow rate of the solution A in the step (3) is 0.1-2000 mu L/min; the flow rate of the solution B is 0.1-2000 mu L/min; and after the solutions A and B enter the microchannel reactor module I, the reaction time is 1-600 s.
7. The method of claim 1, wherein: the heteropoly acid in the step (4) is one or more of heteropoly acid with a Keggin structure and derivatives thereof, the concentration of the solution C is 0.01-10mol/L, and the flow rate of the solution C is 0.1-2000 mu L/min.
8. The method of claim 1, wherein: the magnetic oxide in the step (4) is one or more of ferroferric oxide, ferric oxide, chromium dioxide and cobaltosic oxide, the concentration of the solution D is 0.01-10mol/L, and the flow rate of the solution D is 0.1-2000 mu L/min.
9. The method of claim 1, wherein: the flow rate of the product feed liquid containing the MOFs crystal seeds sent into the micro-channel reactor module II in the step (4) is 0.2-2000 mu L/min; the reaction time of the module II is 1-600 s.
10. The method of claim 1, wherein: the flow rate of the solution B in the step (5) is 0.1-2000 mu L/min; the reaction time of the module III is 1-600 s.
11. The method of claim 1, wherein: and (5) adding acid into the solution B to adjust the pH value of the reaction system to 1-7.
12. A magnetic heteropoly acid catalyst is characterized in that: prepared by the method of any one of claims 1 to 11, wherein the proportion of the metal organic framework material in the catalyst is 30 to 80 weight percent, the proportion of the heteropoly acid is 10 to 45 weight percent, the proportion of the magnetic substance is 5 to 20 weight percent, and the specific surface area is 700-1200 m-2The ratio of medium strong acid/weak acid is 2-12, and the ratio of medium strong acid/strong acid is 2-8.
13. Use of a catalyst according to claim 12, characterized in that: the magnetic heteropolyacid catalyst is used as a heterogeneous magnetic catalyst and is applied to alkylation, isomerization, esterification or catalytic oxidation reactions.
14. Use of a catalyst according to claim 13, characterized in that: the magnetic heteropolyacid catalyst is applied to the reaction of synthesizing 5-hydroxymethylfurfural by preparing glucose.
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