CN108114748A - A kind of magnetic heteropolyacid catalyst and preparation method thereof - Google Patents
A kind of magnetic heteropolyacid catalyst and preparation method thereof Download PDFInfo
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- 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
- C07D307/38—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Abstract
The present invention relates to a kind of magnetic heteropolyacid catalyst and preparation method thereof, including（1）Metal precursor is added in into obtained solution A in organic solvent；（2）Organic ligand is added in into obtained solution B in organic solvent；（3）Solution A and B are sent into in-situ preparation MOFs crystal seeds in micro passage reaction module I by certain flow rate；（4）Heteropoly acid is added to the water stirring, obtained solution C；Magnetic oxide is added to the water stirring, obtained solution D；In step（3）When feed liquid is entered in module ii, solution C, solution D are sent by certain flow rate in module ii；（5）In step（4）When feed liquid enters module III, solution B is sent by certain flow rate in module III, the reaction of crystal seed revulsive crystallization is completed under ultrasound condition, magnetic heteropolyacid catalyst is made.The present invention prepares magnetic heteropolyacid catalyst using micro passage reaction combination ultrasound condition, and heteropoly acid and magnetic material dispersiveness, preparation time is short, production efficiency is high.
Description
Technical field
The present invention relates to heteropolyacid catalysts, and in particular to a kind of magnetic heteropolyacid catalyst and preparation method thereof.
Background technology
Heteropoly acid is the multi-metal oxygen cluster compound of transition metal composition before one kind, and structure can be in molecule or the water of atom
It puts down, have a wide range of applications in fields such as catalysis, electrochemistry, bioscience and material science.Heteropoly acid is a kind of
Excellent homogeneous catalysis material, however hardly possible is separated from liquid phase reaction medium.Therefore, scholars pay close attention to the multiphase of heteropoly acid always
Chemical industry is made.Since the specific surface area of heteropoly acid is relatively low, thus research heteropoly acid package carrier has important practical application meaning.
At present, more common heteropoly acid package carrier has silica, activated carbon, silica gel, resin, mesopore molecular sieve, TiO2Deng.
Metal-organic framework materials（MOFs）, metal coordinating polymer is also known as, is referred to inorganic metal or metal cluster with containing
The crystalline material that the multiple tooth organic ligand of nitrogen oxygen is formed by being coordinated key connection is a kind of with high-specific surface area, adjustable variable orifice
Road size, the porous material of organic functional.Since MOF materials can select not according to different heteropoly acid particle size
Same organic ligand and metal ion builds the duct of different size and structure, so selecting MOF materials in recent years as encapsulation
Heteropoly acid it is of increased attention.
CN103769036 discloses a kind of compound based on Keggin-type poly-tungstate and molecule based porous materials MIL-101
The preparation method of material and its application of Dye Adsorption, by tetramethylammonium hydroxide, terephthalic acid (TPA), chromic nitrate, Keggin-type
Poly-tungstate compound and water are mixed according to certain mass ratio, are put into autoclave, react 2-3 at 175-185 DEG C
My god, it is cooled to room temperature, cleans that obtain poly-tungstate MIL-101 compound with deionized water and n,N-Dimethylformamide respectively
Material.Obtained material can be used for the absorption of Cationic organic dyes, to the adsorption rate of methylene blue up to 98% in the short time,
Its adsorption effect is apparently higher than simple MIL-101 materials, higher than the adsorption capacity of activated carbon.
CN103191786 discloses a kind of MIL-100（Fe）The preparation method of phosphorus heteropoly tungstic acid catalyzer is encapsulated, by phosphorus tungsten
The raw material of heteropoly acid is added in by proportioning in a certain amount of deionized water, then adds in a certain amount of source of iron, is mixed, is added one
Quantitative organic ligand adds in a certain amount of acid solution after mixing, be mixed；Then mixed at normal pressure, 80-95 DEG C
Conjunction is stirred to react 5-20h；Obtained solid is filtered, 10-20h is washed at 60-80 DEG C with absolute ethyl alcohol, then uses 30-
The ammonium fluoride solution of 60mmol/L handles 10-15h at 60-80 DEG C, is then fully washed with deionized water, finally in 100-200
Dry 5-10h is to get to MIL-100 at DEG C（Fe）Encapsulate phosphorus heteropoly tungstic acid catalyzer.
The above-mentioned method for preparing heteropolyacid catalyst is intermittent reaction synthetic method, and there are the reaction time in preparation process
Long, the shortcomings of properties of product are unstable, it is unfavorable for the amplification production of product large-scale industrial.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of magnetic heteropolyacid catalysts and preparation method thereof.This hair
It is bright that magnetic heteropolyacid catalyst is prepared using micro passage reaction combination ultrasound condition, it can obtain that particle diameter distribution is narrow, heteropoly acid
With the product of magnetic material good dispersion, and can shorten preparation time, improve production efficiency.
The preparation method of magnetic heteropolyacid catalyst of the present invention, includes the following steps：
（1）Metal precursor is added in into stirring and dissolving in organic solvent, obtained solution A；
（2）Organic ligand is added in into stirring and dissolving in organic solvent, obtained solution B；
（3）Solution A and B are respectively fed to in-situ preparation MOFs crystal seeds in micro passage reaction module I according to certain flow velocity, instead
Product feed liquid should be sent into micro passage reaction module ii after a certain period of time；
（4）Heteropoly acid is added to the water stirring, obtained solution C；Magnetic oxide is added to the water stirring, obtained solution D；In step
Suddenly（3）When gained feed liquid is entered in module ii, solution C, solution D are sent into according to certain flow velocity in module ii, reaction is certain
Product feed liquid is sent into micro passage reaction module III after time；
（5）In step（4）When gained feed liquid enters module III, solution B is sent into according to certain flow velocity in module III, in ultrasound
Under the conditions of complete the reaction of crystal seed revulsive crystallization, magnetic heteropolyacid catalyst suspension is made；
（6）By step（5）Magnetic heteropolyacid suspension obtained carries out separation of solid and liquid, and solid is washed with ethyl alcohol, at 80~120 DEG C
Lower drying 8~for 24 hours.
Step of the present invention（1）The metal precursor is the sulfuric acid of copper, iron, zirconium, zinc, magnesium, aluminium, cobalt, chromium, nickel, calcium, titanium
One or more of salt, nitrate, acetate, carbonate, halide salt or its hydrate are preferably iron chloride.It is described organic
Solvent is water, methanol, ethyl alcohol, isopropanol, ethylene glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N- diethyl
One or more of formamide, N, N- diethyl acetamides, preferably water, methanol or ethyl alcohol, more preferable water.The solution A
The concentration of middle metal precursor is 0.01-5.0mol/L, is preferably 0.1-2.0mol/L.
Step of the present invention（2）The organic ligand is multiple tooth organic compound, is preferably bidentate, three tooth Carboxylic acid ligand chemical combination
Object and its derivative, including terephthalic acid (TPA), M-phthalic acid, trimesic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids,
2,6- naphthalene dicarboxylic acids etc. are preferably trimesic acid；Derivative refers to one or more carboxylic-acid functionals in Carboxylic acid ligand compound
Group is substituted by functional groups such as nitryl group, hydroxyl group, methyl group, cyano groups.The organic solvent for methanol, ethyl alcohol,
Isopropanol, ethylene glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N- diethylformamides, N, N- diethyl second
One or more of amide is preferably methanol, ethyl alcohol or isopropanol, more preferably isopropanol.Organic ligand in the solution B
Concentration for 0.01-10mol/L, be preferably 0.1-2.0mol/L.
Step of the present invention（3）The flow velocity of the solution A is 0.1-2000 μ l/min, is preferably 5-200 μ l/min.Solution B
Flow velocity for 0.1-2000 μ l/min, be preferably 5-200 μ l/min.After the solution A and B enter micro passage reaction module I,
Reaction temperature is 30-80 DEG C, is preferably 50-70 DEG C, reaction pressure 0.1-2.0MPa, is preferably 0.1-1.0MPa, during reaction
Between for 1-600s, be preferably 30-180s.
Step of the present invention（4）The heteropoly acid is the heteropoly acid of structure with Keggin and its one or more of derivative,
Preferably phosphotungstic acid, phosphomolybdic acid, tungstosilicic acid, molybdenum silicic acid, sodium phosphotungstate, ammonium phosphotungstate, silver phosphotungstate, ammonium phosphomolybdate, phosphomolybdic acid
Sodium, phosphomolybdic acid silver, tungstosilicic acid sodium, tungstosilicic acid ammonium, tungstosilicic acid silver, molybdenum silicic acid sodium, molybdenum silicic acid copper, more preferably phosphotungstic acid.It is described
The concentration of solution C is 0.01-10mol/L, is preferably 0.05-0.5mol/L.The flow velocity of solution C is 0.1-2000 μ l/min, excellent
Elect 5-100 μ l/min as.
Step of the present invention（4）The magnetic oxide is ferroso-ferric oxide, di-iron trioxide, chromium dioxide, four oxidations three
One or more of cobalt etc. is preferably ferroso-ferric oxide.The concentration of solution D is 0.01-10mol/L, is preferably 0.05-
0.1mol/L.The flow velocity of solution D is 0.1-2000 μ l/min, is preferably 5-100 μ l/min.
Step of the present invention（4）The flow velocity that product feed liquid containing MOFs crystal seeds is sent into micro passage reaction module ii is 0.2-
2000 μ l/min are preferably 10-400 μ l/min.Step（4）The reaction temperature of the module ii is 30-150 DEG C, is preferably 70-
110 DEG C, reaction pressure 0.1-2.0MPa, be preferably 0.1-1.0MPa, reaction time 1-600s, is preferably 60-240s.
Step of the present invention（5）The flow velocity of the solution B is 0.1-2000 μ l/min, is preferably 5-200 μ l/min.The mould
The reaction temperature of block III is 80-200 DEG C, is preferably 120-180 DEG C；Reaction pressure is 0.1-2.0MPa, is preferably 0.1-
1.0MPa；Reaction time is 1-600s, is preferably 60-300s.
Step of the present invention（5）The frequency of the ultrasonic wave is 20-100KHz, and power is 120-800W.
Step of the present invention（6）The magnetic heteropolyacid suspension completes solid-liquid point by means such as high speed centrifugation or suction filtrations
From.
Step of the present invention（3）And step（5）The middle acid that added in into solution B adjusts the pH value of reaction system as 1-7, is preferably
2-4.The acid can be hydrochloric acid, acetic acid, citric acid, hydrofluoric acid, sulfuric acid, be preferably hydrochloric acid.MOFs crystal seeds are generated in the original location
And the pH value that reaction system is adjusted in crystal seed Induction Process contributes in module I MOFs in MOF crystal seeds, module ii between 2-4
The generation and growth of crystal.
Micro passage reaction module I of the present invention, module ii, module III are cascade, according to actual production need
Will, it can in parallel several module Is, module ii, III tandem reactor of module.The material of the reactor for special glass, ceramics,
Polytetrafluoroethylene (PTFE), stainless steel or alloy etc..The structure of reactor can be with intensified response object object for cardioid, diamond shape, rectangle etc.
The shape of mixing is flowed, reactor inside diameter is 10-2000 microns.The micro passage reaction module include at least two feed inlets and
One discharge port can require to change feed inlet quantity and position according to reaction.
Magnetic heteropolyacid catalyst of the present invention is prepared using the invention described above method, there is metal in catalyst
Machine framework material accounting is 30wt%-80wt%, and heteropoly acid accounting is 10wt%-45wt%, and the accounting of magnetic material is 5wt %-20wt
%, specific surface area 700-1200m2/ g, middle strong acid/weak acid ratio is 2-12, and middle strong acid/strong acid ratio is 2-8.
The application of magnetic heteropolyacid catalyst of the present invention can be used as heterogeneous magnetic catalyst, applied to alkane
In the reactions such as base, isomerization, esterification, catalysis oxidation, it is especially applied to glucose and prepares synthesis 5 hydroxymethyl furfural reaction
In.
Compared with prior art, the method for the present invention has following outstanding advantages：
（1）The present invention prepares magnetic heteropolyacid catalyst using micro passage reaction combination ultrasound condition, can obtain grain size point
Cloth is narrow, heteropoly acid and magnetic material good dispersion, reuses the good catalyst prod of effect, and can shorten preparation time,
Improve the utilization rate of heteropoly acid and magnetic material.Compared with the preparation method of similar product, simple with preparation process, the cycle is short
Feature, more suitable for industrialized mass production.
（2）The reactor that micro passage reaction is made of multiple microchannel modules has high mass transfer, the spy of high heat transfer
Point, the present invention encapsulate heteropoly acid, the conventional method encapsulation heteropoly acid of solution while preparing metal-organic framework materials in the original location
Deficiency, heteropoly acid is not easily decomposed, and packaging effect is good.
（3）Strong acid/weak acid, middle strong acid/strong acid during ultrasound condition combination multimode micro passage reaction can be controlled accurately
Ratio, so as to prepare the heteropolyacid catalyst of suitable catalytic reaction acid distribution.
Description of the drawings
Fig. 1 is the structure diagram for the three module micro passage reactions that the method for the present invention uses；
Wherein 1,2 be the feed inlet of module I, and 3 be the discharge port of module I, and 4,5 be the feed inlet of module ii, and 6 be going out for module ii
Material mouth, 7,8 be the feed inlet of module III, and 9 be the discharge port of module III.
Fig. 2 is 1-5 of the embodiment of the present invention, comparative example 1-3 synthetic catalysts and MIL-100 (Fe) and Fe3O4XRD diagram.
Fig. 3 is the SEM figures of 3 synthetic sample of the method for the present invention embodiment.
Specific embodiment
With reference to embodiment and comparative example, the present invention is further illustrated, but protection scope of the present invention and from
The limitation of embodiment.Reagent and material described in following embodiments and comparative example, unless otherwise specified, are commercially obtained
.
The embodiment of the present invention is using three module micro passage reactions, as shown in Figure 1.Idiographic flow is by metal front
Body, which is dissolved in organic solvent, forms solution A, and organic ligand is dissolved in organic solvent and forms solution B, heteropoly acid is dissolved
Yu Shuizhong forms solution C, and magnetic oxide and water are stirred to form solution D.Solution A and solution B are according to certain flow velocity
By feed inlet 1,2 into hybrid reaction in module I, the feed liquid containing MOFs crystal seeds is formed under certain temperature, pressure, from discharging
3 outflow of mouth enters from feed inlet 4 in module ii according to certain flow velocity, and C solution, the solution D entered with feed inlet 5 mixes instead
Should, it is reacted under certain temperature, pressure after a certain period of time, is flowed out from discharge port 6 and enter mould from charge door 7 according to certain flow velocity
In block III, the B solution hybrid reaction with the entrance of feed inlet 8 completes the reaction of crystal seed revulsive crystallization under conditions, is made magnetic miscellaneous more
Acid catalyst suspension.The suspension of acquisition is finally subjected to separation of solid and liquid, solid is washed with ethyl alcohol, is done at 80~120 DEG C
Dry 8~for 24 hours.
The micro passage reaction that the embodiment of the present invention uses is commercially available micro passage reaction, and the material of reactor is stainless
Steel, structure are cardioid, and reactor inside diameter is 10-2000 microns.
The conveying equipment of reaction solution described in the embodiment of the present invention is high pressure pump, using III types of 305SFM01, pressure
Scope 0-6000psi, flow control accuracy 0.2%, flow rates 0.001-5ml/min.
In the present invention, the granule size distribution curve that particle diameter distribution tests to obtain particle by particle diameter distribution instrument calculates
It arrives.Loaded by heteropoly acid and dispersiveness are obtained by XRD and BET data Conjoint Analysis；The utilization rate of heteropoly acid：Feed intake middle heteropoly acid
The ratio of quality and heteropoly acid quality difference value in residual liquid and the middle heteropoly acid quality that feeds intake, wherein the quality for the middle heteropoly acid that feeds intake
Pass through chromatographic quantitative analysis with heteropoly acid quality in residual liquid；The ratio of middle strong acid and strong acid, middle strong acid and weak acid passes through
NH3-TPD analyses data obtain.Magnetic material loads and dispersiveness is obtained by XRD and BET data Conjoint Analysis；The profit of magnetic material
With rate：The ratio of the magnetic material quality that feeds intake and magnetic material quality difference value in residual liquid and the middle magnetic material quality that feeds intake, wherein
Feed intake magnetic material quality and residual liquid in magnetic material quality pass through chromatographic quantitative analysis.
Embodiment 1
13.52g ferric trichlorides are dissolved in 500ml water and form solution A, it is different that 10.51g trimesic acids are dissolved in 500ml
Solution B is formed in propyl alcohol, 71.2g phosphotungstic acids are dissolved in 500ml water and form solution C, by 5.8g ferroso-ferric oxides and 500ml
Water is stirred to form solution D.By solution A and solution B according to flow velocity be 5 μ l/min, be sent into micro passage reaction module I in
In-situ preparation MOFs crystal seeds, the reaction temperature of module I is 50 DEG C, and pressure 0.1MPa, the residence time is 30s, raw in module I
It into the feed liquid containing MOFs crystal seeds, is sent into micro passage reaction module ii, flow velocity is 10 μ l/min；By solution C with flow velocity 5
μ l/min are sent into micro passage reaction module ii, while solution D liquid are sent by 5 μ l/min of flow velocity in module ii, reaction
Temperature is 70 DEG C, pressure 0.1MPa, residence time 60s, and product feed liquid is sent into module III, and flow velocity is 20 μ l/min, will
Solution B is sent by 5 μ l/min of flow velocity in module III, and wherein the reaction temperature of module III is 120 DEG C, and pressure 0.1MPa stops
It is 60s to stay the time, and the frequency of ultrasonic wave is 20KHz, and power is 120W, and magnetic heteropolyacid catalyst suspension is made.By gained
Product feed liquid separation of solid and liquid, solid are washed with ethyl alcohol, are dried for 24 hours at 100 DEG C, are obtained magnetic heteropolyacid catalyst.
The sample is shown as magnetic metal organic framework material package heteropolyacid catalyst through XRD characterization, it is miscellaneous in catalyst
Polyacid load capacity is 23wt%, magnetic material content 15wt%, specific surface area 815m2/ g, middle strong acid/weak acid ratio is 2.3, in it is strong
Acid/strong acid ratio is that 2.2,0.3-0.5 μm of particle diameter distribution is 68%, and heteropoly acid utilization rate is 75%, and magnetic material utilization rate is
80%。
Embodiment 2
135.29g ferric trichlorides are dissolved in 500ml water and form solution A, 210.24g trimesic acids are dissolved in 500ml
Solution B is formed in isopropanol, 712g phosphotungstic acids are dissolved in 500ml water and form solution C, by 11.57g ferroso-ferric oxides with
500ml water is stirred to form solution D.By solution A and solution B according to flow velocity be 200 μ l/min, be sent into micro passage reaction
In-situ preparation MOFs crystal seeds in module I, the reaction temperature of module I is 70 DEG C, and pressure 1.0MPa, the residence time is 180s,
The feed liquid containing MOFs crystal seeds is generated in module I, is sent into micro passage reaction module ii, flow velocity is 400 μ l/min；It will be molten
Liquid C is sent into 100 μ l/min of flow velocity in micro passage reaction module ii, while solution D liquid is sent by 100 μ l/min of flow velocity
In module ii, reaction temperature is 110 DEG C, pressure 1.0MPa, residence time 240s, and product feed liquid is sent into module III, stream
Speed is 400 μ l/min, solution B is sent by 200 μ l/min of flow velocity in module III, wherein the reaction temperature of module III is 80
DEG C, pressure 1.0MPa, the residence time is 300s, and the frequency of ultrasonic wave is 100KHz, and power is 800W, and magnetic heteropolyacid is made
Catalyst suspension.By products therefrom feed liquid separation of solid and liquid, solid is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C, is obtained magnetism
Heteropolyacid catalyst.
The sample is shown as magnetic metal organic framework material package heteropolyacid catalyst through XRD characterization, it is miscellaneous in catalyst
Polyacid load capacity is 16wt%, magnetic material content 10wt%, specific surface area 824m2/ g, middle strong acid/weak acid ratio is 2.0, in it is strong
Acid/strong acid ratio is that 4.4,2-3 μm of particle diameter distribution is 72%, and heteropoly acid utilization rate is 80%, and magnetic material utilization rate is 83%.
Embodiment 3
48.13g ferric trichlorides are dissolved in 500ml water and form solution A, it is different that 100.34g trimesic acids are dissolved in 500ml
Solution B is formed in propyl alcohol, 189.5g phosphotungstic acids are dissolved in 500ml water and form solution C, by 8.9g ferroso-ferric oxides with
500ml water is stirred to form solution D.By solution A and solution B according to flow velocity be 100 μ l/min, be sent into micro passage reaction
In-situ preparation MOFs crystal seeds in module I, the reaction temperature of module I is 60 DEG C, and pressure 0.5MPa, the residence time is 120s,
The feed liquid containing MOFs crystal seeds is generated in module I, is sent into micro passage reaction module ii, flow velocity is 200 μ l/min；It will be molten
Liquid C is sent into 50 μ l/min of flow velocity in micro passage reaction module ii, while solution D liquid is sent into mould by 50 μ l/min of flow velocity
In block II, reaction temperature is 100 DEG C, pressure 0.5MPa, residence time 120s, and product feed liquid is sent into module III, flow velocity
For 300 μ l/min, solution B is sent by 100 μ l/min of flow velocity in module III, wherein the reaction temperature of module III is 160 DEG C,
Pressure is 0.5MPa, and the residence time is 200s, and the frequency of ultrasonic wave is 80KHz, and power is 500W, and magnetic heteropolyacid catalysis is made
Agent suspension.By products therefrom feed liquid separation of solid and liquid, solid is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C, is obtained magnetic miscellaneous more
Acid catalyst.
The sample is shown as magnetic metal organic framework material package heteropolyacid catalyst through XRD characterization, it is miscellaneous in catalyst
Polyacid load capacity is 45wt%, magnetic material content 19wt%, specific surface area 1135m2/ g, middle strong acid/weak acid ratio is 10.0, in
Strong acid/strong acid ratio is that 6.6,1.0-1.5 μm of particle diameter distribution is 90%, and heteropoly acid utilization rate is 92%, and magnetic material utilization rate is
90%。
Embodiment 4
Process flow and operating condition are same as Example 1.Difference is：Nitric acid is added in into solution B and adjusts reaction system
PH value is 2.5.After reaction, product feed liquid is collected, is centrifuged, is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.Through XRD
Characterization shows the sample as magnetic metal organic framework material package heteropolyacid catalyst, and in catalyst, loaded by heteropoly acid amount is
25wt%, magnetic material content 16wt%, specific surface area 975m2/ g, middle strong acid/weak acid ratio is 5.1, middle strong acid/strong acid ratio
The particle diameter distribution for being 7.6,0.3-0.5 μm is 80%, and heteropoly acid utilization rate is 83%, and magnetic material utilization rate is 85%.
Embodiment 5
Process flow and operating condition are same as Example 1.Difference is：Citric acid is added in into solution B and adjusts reaction system
PH value be 4.After reaction, product feed liquid is collected, is centrifuged, is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.Through XRD
Characterization shows the sample as magnetic metal organic framework material package heteropolyacid catalyst, and in catalyst, loaded by heteropoly acid amount is
27wt%, magnetic material content 17wt%, specific surface area 927m2/ g, middle strong acid/weak acid ratio is 2.5, middle strong acid/strong acid ratio
The particle diameter distribution for being 5.8,0.3-0.5 μm is 75%, and heteropoly acid utilization rate is 78%, and magnetic material utilization rate is 82%.
Embodiment 6
Process flow and operating condition are same as Example 1.Difference is：In solution A metal precursor be copper nitrate, You Jirong
Agent is ethyl alcohol；Organic ligand is terephthalic acid (TPA) in solution B, and organic solvent is ethyl alcohol.After reaction, product feed liquid is collected,
It is centrifuged, is washed with ethyl alcohol, dried for 24 hours at 100 DEG C.Show that the sample is magnetic metal organic framework material through XRD characterization
Material encapsulation heteropolyacid catalyst, in catalyst, loaded by heteropoly acid amount is 20wt%, magnetic material content 10wt%, and specific surface area is
785m2/ g, middle strong acid/weak acid ratio is 2.8, and middle strong acid/strong acid ratio is that 5.6,0.3-0.5 μm of particle diameter distribution is 60%, miscellaneous
Polyacid utilization rate is 65%, and magnetic material utilization rate is 70%.
Embodiment 7
Process flow and operating condition are same as Example 1.Difference is：Heteropoly acid is phosphomolybdic acid in solution C.Reaction terminates
Afterwards, product feed liquid is collected, is centrifuged, is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.Show that the sample is magnetic through XRD characterization
Property metal-organic framework materials encapsulation heteropolyacid catalyst, in catalyst, loaded by heteropoly acid amount is 15wt%, magnetic material content
12wt%, specific surface area 750m2/ g, middle strong acid/weak acid ratio is 4.1, and middle strong acid/strong acid ratio is 6.8,0.3-0.5 μm
Particle diameter distribution is 57%, and heteropoly acid utilization rate is 60%, and magnetic material utilization rate is 75%.
Embodiment 8
Process flow and operating condition are same as Example 1.Difference is：Magnetic material is cobaltosic oxide in solution D.Reaction knot
Shu Hou collects product feed liquid, is centrifuged, washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.Show that the sample is through XRD characterization
Magnetic metal organic framework material package heteropolyacid catalyst, in catalyst, loaded by heteropoly acid amount is 18wt%, magnetic material content
14wt%, specific surface area 730m2/ g, middle strong acid/weak acid ratio is 3.5, and middle strong acid/strong acid ratio is 8.9,1.0-1.5 μm
Particle diameter distribution is 62%, and heteropoly acid utilization rate is 63%, and magnetic material utilization rate is 68%.
Comparative example 1
Process flow and operating condition are same as Example 3.Difference is：Micro passage reaction module I, module ii, module III
In reaction condition it is identical, reaction temperature is 160 DEG C, pressure 1.0MPa.After reaction, separation of solid and liquid, filter cake are carried out
It is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.Show that the sample is miscellaneous more for magnetic metal organic framework material package through XRD characterization
Acid catalyst, in catalyst, loaded by heteropoly acid amount is 12wt%, magnetic material content 9wt%, specific surface area 635m2/ g, in it is strong
Acid/weak acid ratio is 2.9, and middle strong acid/strong acid ratio is that 3.1,1.0-1.5 μm of particle diameter distribution is 55%, and heteropoly acid utilization rate is
58%, magnetic material utilization rate is 61%.
Comparative example 2
Process flow and operating condition are same as Example 3.Difference is：Micro passage reaction module I, module ii, module III
In reaction condition it is identical, reaction temperature is 60 DEG C, pressure 0.5MPa.After reaction, separation of solid and liquid is carried out, filter cake is used
Ethyl alcohol washs, and is dried for 24 hours at 100 DEG C.Show that the sample is magnetic metal organic framework material package heteropoly acid through XRD characterization
Catalyst, in catalyst, loaded by heteropoly acid amount is 11wt%, magnetic material content 8wt%, specific surface area 621m2/ g, middle strong acid/
Weak acid ratio is 2.6, and middle strong acid/strong acid ratio is that 1.7,1.0-1.5 μm of particle diameter distribution is 53%, and heteropoly acid utilization rate is
55%, magnetic material utilization rate is 57%.
Comparative example 3
Process flow and operating condition are same as Example 3.Difference is：Micro passage reaction module III does not have ultrasonic response
Condition.After reaction, separation of solid and liquid is carried out, filter cake is washed with ethyl alcohol, is dried for 24 hours at 100 DEG C.This is shown through XRD characterization
Sample is magnetic metal organic framework material package heteropolyacid catalyst, and in catalyst, loaded by heteropoly acid amount is 10wt%, magnetic
Object content 5wt%, specific surface area 416m2/ g, middle strong acid/weak acid ratio is 1.6, and middle strong acid/strong acid ratio is 2.4,1.0-
1.5 μm of particle diameter distribution is 48%, and heteropoly acid utilization rate is 47%, and magnetic material utilization rate is 45%.
Catalyst prepared by above-described embodiment 1-3 and comparative example 1-3 prepares synthesis 5 hydroxymethyl furfural for glucose.
The using effect of 1 embodiment 1-3 of table and comparative example 1-3 catalyst
By table 1, the embodiment of the present invention prepare in catalyst prepares for glucose 5 hydroxymethyl furfural reaction, turn
Rate is higher, and it is good to reuse effect.
Claims (15)
1. a kind of preparation method of magnetic heteropolyacid catalyst, it is characterised in that include the following steps：
（1）Metal precursor is added in into stirring and dissolving in organic solvent, obtained solution A；
（2）Organic ligand is added in into stirring and dissolving in organic solvent, obtained solution B；
（3）Solution A and B are respectively fed to in-situ preparation MOFs crystal seeds in micro passage reaction module I according to certain flow velocity, instead
Product feed liquid should be sent into micro passage reaction module ii after a certain period of time；
（4）Heteropoly acid is added to the water stirring, obtained solution C；Magnetic oxide is added to the water stirring, obtained solution D；In step
Suddenly（3）When gained feed liquid is entered in module ii, solution C, solution D are sent into according to certain flow velocity in module ii, reaction is certain
Product feed liquid is sent into micro passage reaction module III after time；
（5）In step（4）When gained feed liquid enters module III, solution B is sent into according to certain flow velocity in module III, in ultrasound
Under the conditions of complete the reaction of crystal seed revulsive crystallization, magnetic heteropolyacid catalyst suspension is made；
（6）By step（5）Magnetic heteropolyacid suspension obtained carries out separation of solid and liquid, and solid is washed with ethyl alcohol, at 80~120 DEG C
Lower drying 8~for 24 hours.
2. according to the method described in claim 1, it is characterized in that：Step（1）The metal precursor be copper, iron, zirconium, zinc,
Magnesium, aluminium, cobalt, chromium, nickel, calcium, the sulfate of titanium, nitrate, acetate, carbonate, halide salt or one kind in its hydrate or
It is several；The organic solvent is water, methanol, ethyl alcohol, isopropanol, ethylene glycol, isobutanol, glycerine, N, N- dimethyl formyls
One or more of amine, N, N- diethylformamides, N, N- diethyl acetamides；Metal precursor in the solution A
Concentration is 0.01-5.0mol/L.
3. method according to claim 1 or 2, it is characterised in that：Step（1）The metal precursor iron chloride, it is described
Organic solvent is water, and the concentration of metal precursor is 0.1-2.0mol/L in the solution A.
4. according to the method described in claim 1, it is characterized in that：Step（2）The organic ligand is bidentate, three tooth carboxylate ligands
Body compound and its derivative, including terephthalic acid (TPA), M-phthalic acid, trimesic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5- naphthalenes two
Carboxylic acid or 2,6- naphthalene dicarboxylic acids, derivative refer in Carboxylic acid ligand compound one or more carboxylic acid functionals by nitryl group,
The functional groups such as hydroxyl group, methyl group, cyano group substitute；The organic solvent for methanol, ethyl alcohol, isopropanol, ethylene glycol,
Isobutanol, glycerine, N,N-dimethylformamide, N, N- diethylformamides, N, one kind in N- diethyl acetamides or
It is several；The concentration of organic ligand is 0.01-10mol/L in the solution B.
5. the method according to claim 1 or 4, it is characterised in that：Step（2）The organic ligand is trimesic acid,
The organic solvent is isopropanol, and the concentration of organic ligand is 0.1-2.0mol/L in the solution B.
6. according to the method described in claim 1, it is characterized in that：Step（3）The flow velocity of the solution A is 0.1-2000 μ l/
min；The flow velocity of solution B is 0.1-2000 μ l/min；After the solution A and B enter micro passage reaction module I, reaction temperature
For 30-80 DEG C, reaction pressure 0.1-2.0MPa, reaction time 1-600s.
7. according to the method described in claim 1, it is characterized in that：Step（4）The heteropoly acid is miscellaneous more for structure with Keggin
One or more of acid and its derivative, the concentration of the solution C is 0.01-10mol/L, and the flow velocity of solution C is 0.1-
2000μl/min。
8. according to the method described in claim 1, it is characterized in that：Step（4）The magnetic oxide is ferroso-ferric oxide, three
Aoxidize one or more of two iron, chromium dioxide, cobaltosic oxide etc., the concentration of solution D is 0.01-10mol/L, solution D
Flow velocity be 0.1-2000 μ l/min.
9. according to the method described in claim 1, it is characterized in that：Step（4）Product feed liquid containing MOFs crystal seeds is sent into micro-
The flow velocity of channel reactor module ii is 0.2-2000 μ l/min；The reaction temperature of the module ii is 30-150 DEG C, reaction pressure
Power be the 0.1-2.0MPa reaction time be 1-600s.
10. according to the method described in claim 1, it is characterized in that：Step（5）The flow velocity of the solution B is 0.1-2000 μ l/
min；The reaction temperature of module III is 80-200 DEG C, reaction pressure 0.1-2.0MPa, reaction time 1-600s.
11. according to the method described in claim 1, it is characterized in that：Step（5）The frequency of the ultrasonic wave is 20-100KHz,
Power is 120-800W.
12. according to the method described in claim 1, it is characterized in that：Step（3）And step（5）The middle acid that added in into solution B is adjusted
The pH value for saving reaction system is 1-7.
13. a kind of magnetic heteropolyacid catalyst, it is characterised in that：It is to be prepared using the invention described above method, it is golden in catalyst
It is 30wt%-80wt% to belong to organic framework material accounting, and heteropoly acid accounting is 10wt%-45wt%, and the accounting of magnetic material is 5wt %-
20wt %, specific surface area 700-1200m2/ g, middle strong acid/weak acid ratio is 2-12, and middle strong acid/strong acid ratio is 2-8.
14. the application of catalyst described in claim 13, it is characterised in that：The magnetic heteropolyacid catalyst is as heterogeneous magnetic
Property catalyst, applied in alkylation, isomerization, esterification, catalytic oxidation.
15. the application of catalyst according to claim 14, it is characterised in that：The magnetic heteropolyacid catalyst is applied to Portugal
Grape sugar is prepared in synthesis 5 hydroxymethyl furfural reaction.
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