CN112206784B - Application of metal mesh supported metal particle catalyst in catalytic synthesis of pterostilbene - Google Patents
Application of metal mesh supported metal particle catalyst in catalytic synthesis of pterostilbene Download PDFInfo
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Abstract
The invention provides an application of a metal mesh supported metal particle catalyst in a reaction for catalyzing and synthesizing pterostilbene by taking bromoaryl propiophenone shown in a formula (I) and a styrene derivative shown in a formula (II) as raw materials; the metal mesh supported metal particle catalyst is prepared by a preparation method comprising the following steps: (1) Weighing metal precursors with corresponding mass, and then dissolving the metal precursors with 25-28% ammonia water to prepare impregnating solution; (2) Removing greasy dirt and an oxidation layer on the surface of the metal wire mesh, and immersing the metal wire mesh in deionized water for standby after treatment; (3) Immersing the wire mesh in an immersion liquid, wherein the immersion liquid is in a vigorously stirred state, and then applying intermittent microwave treatment to the immersion liquid; (4) And (3) cleaning the metal wire mesh loaded in the step (3) by deionized water, drying in the shade, and roasting at 200-500 ℃ for 1-5 hours in an inert atmosphere to obtain the metal particle catalyst loaded on the metal wire mesh. The catalyst of the invention has excellent conversion rate and selectivity in the application process.
Description
Technical Field
The invention particularly relates to an application of a metal mesh supported metal particle catalyst in a pterostilbene catalytic synthesis reaction by taking bromoaryl propiophenone and styrene as raw materials.
Background
Pterostilbene, the chemical name of which is (E) -3, 5-dimethoxy-4' -hydroxy stilbene, is a derivative of resveratrol, has antifungal activity stronger than resveratrol, and has the activities of resisting oxidation, scavenging free radicals in vivo and the like. The pterostilbene can reduce the blood fat and blood sugar content, prevent breast cancer, heart disease and the like, and has good application prospect. The natural pterostilbene is derived from plants such as the dragon's blood, the blueberries, the grapes, the propolis and the like in Guangxi, but the natural product has low content and high extraction cost, and the components are easily damaged in the extraction process, so that the wide application of the pterostilbene is limited.
A method for synthesizing pterostilbene and derivatives thereof is disclosed in Chinese patent CN105367390B, and under the protection of nitrogen, cinnamic acid derivatives are used as raw materials, N-methyl-2-pyrrolidone is used as a solvent, and Cs is used as a solvent 2 CO 3 Under the catalysis of the catalyst, the catalyst reacts with bivalent copper ions to generate styryl ketone intermediate, and then Pd (acac) is used for preparing the intermediate 2 Under the catalytic action of the catalyst, the catalyst is heated by microwaves or oil bath, heck decarboxylation coupling reaction is carried out on the catalyst and dimethoxy bromobenzene at 120-150 ℃ to generate pterostilbene and derivatives thereof, finally, dichloroethane water extraction is carried out, an organic layer is taken out, an aqueous layer is extracted and separated by dichloromethane, the organic layers of the two layers are combined, and the final product is obtained by drying magnesium sulfate solid. The reaction condition is mild, the operation is convenient, the trans-form stereoselection is good, the process is still immature, the catalyst cost is high, and the yield and the product purity still have great promotion space. In addition, more Wittig and Wittig-Horner reactions are researched, the operation is simple, the reaction is mild, but the problem of low yield caused by more steps cannot be solved well; the Perkin reaction has good configuration selectivity, but the reaction is harsh, and industrialization is difficult to realize; heck reaction conditions are mild, selectivity is high, and research is paid more attention to in recent years, but the problems of high cost of raw materials and catalysts are prevented from being applied to large-scale industrializationAnd (3) production. Therefore, the existing process is optimized, a process route suitable for pterostilbene industrialization is explored, and the method has important significance for pterostilbene development and popularization.
The existing catalyst using active carbon as carrier has the disadvantages of easy deactivation and easy loss of active components. The metal net has the advantages of reliable filtering precision, regular meshes, accuracy, high temperature resistance, chemical corrosion resistance, strong mechanical property, precise braiding and the like, and is generally an important base material for preparing functional materials. In recent years, it has been known to have special surface properties
The metal mesh also has great application value in the field of catalysis of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problem of providing application of the metal mesh supported metal particle catalyst in the catalytic synthesis of pterostilbene by taking bromoaryl propiophenone and styrene as raw materials.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an application of a metal mesh supported metal particle catalyst in a reaction for catalyzing and synthesizing pterostilbene by taking bromoaryl propiophenone shown in a formula (I) and a styrene derivative shown in a formula (II) as raw materials;
the metal mesh supported metal particle catalyst is prepared by a preparation method comprising the following steps:
(1) Preparing a metal impregnating solution: weighing metal precursors with corresponding mass, and then dissolving the metal precursors with 25-28% ammonia water to prepare impregnating solution; the metal precursor is selected from PdCl 2 、PtCl 4 、NiCl 2 ·6H 2 O、RuCl 3 ·3H 2 At least one of O;
(2) Pretreatment of the wire mesh: removing greasy dirt and an oxidation layer on the surface of the metal wire mesh, and immersing the metal wire mesh in deionized water for standby after treatment; the metal wire is made of copper or copper alloy and one or more than two of zinc, iron, tin and nickel;
(3) Load: immersing a wire mesh in an impregnating solution, wherein the impregnating solution is in a violent stirring state, and then applying intermittent microwave treatment to the impregnating solution, wherein the microwave emission direction is perpendicular to the wire mesh, and the intermittent microwave treatment is specifically as follows: setting microwave frequency at 3-30GHZ, wherein each treatment duration is 1-10S, the interval is 1-10min, and the treatment times are 2-10 times; then adjusting the microwave frequency to be 30GHz to 300GHz, wherein the duration of each treatment is 10-20s, the interval is 1-10min, and the treatment times are 2-10 times;
(4) Post-treatment of the catalyst: and (3) cleaning the metal wire mesh loaded in the step (3) by deionized water, drying in the shade, and roasting at 200-500 ℃ for 1-5 hours in an inert atmosphere to obtain the metal particle catalyst loaded on the metal wire mesh.
In step (1) of the present invention, the pH of the impregnation liquid is controlled to be 7-9, wherein the metal content is 0.01-0.04g/ml.
In the step (2) of the invention, the wire mesh is a mesh woven by wires, preferably, the diameter of the wires is 0.01-1mm, and the mesh size of the woven wire mesh is 0.5-100um. The present invention has no particular requirement on the mesh shape of the wire mesh, and may be a oblong mesh, a square mesh, a circular mesh, etc.
In step (2) of the art, the wire mesh needs to be pretreated to remove oil stains and oxide layers on the surface of the wire mesh, and a person skilled in the art can determine a suitable pretreatment step according to practical situations and conventional operation methods. Preferably, the surface oil stain can be removed by ultrasonic treatment in absolute ethyl alcohol, and then the surface oxide layer can be removed by soaking in dilute hydrochloric acid. It is further preferred that the specific operation of step (2) is: putting the wire mesh into absolute ethyl alcohol, carrying out ultrasonic treatment at 25-30 ℃ for 30-40min to remove oil stains on the surface, and then putting into deionized water for ultrasonic treatment to remove the ethyl alcohol; then put into 1-3mol/L dilute hydrochloric acid for ultrasonic treatment at 25-30 ℃ for 30-40min to remove surface oxide, and finally added into deionized water for ultrasonic treatment to remove acid.
In the step (3), the impregnating solution is placed in a microwave heater for intermittent microwave treatment. Preferably, the power during microwave treatment is 300-400w, the temperature is 100-150 ℃, the stirring speed is 5000-6000rpm, and the stirring Reynolds number Re=800-1500.
In the step (4) of the present invention, the inert atmosphere is preferably a nitrogen or argon atmosphere.
In the step (4), the step of cleaning the wire mesh loaded in the step (3) by deionized water is to quickly transfer the wire mesh into the deionized water after the temperature of the wire mesh is reduced to normal temperature, and then standing for 0.5-5h.
The metal wire mesh supported metal particle catalyst prepared by the invention consists of a metal wire mesh and nano metal particles supported on the metal wire mesh. The size of the loaded nano metal particles is between 1 and 50nm, and the mass content of the loaded nano metal particles in the catalyst is 0.5 to 50 parts per million.
The invention relates to an application of a metal mesh supported metal particle catalyst in a pterostilbene catalytic synthesis reaction by taking bromoaryl propiophenone and a styrene derivative as raw materials, which comprises the following specific steps: the method comprises the steps of taking bromoaryl propiophenone shown in a formula (I) and styrene shown in a formula (II) as raw materials, wherein the mol ratio of the bromoaryl propiophenone to the styrene is 1:0.1-2, injecting the mixture into a micro-channel reactor containing the metal wire mesh supported metal particle catalyst at a flow rate of 0.1-1ml/min after uniform mixing, and reacting at 100-300 ℃ to obtain pterostilbene.
Compared with the prior art, the invention has the following advantages:
1) The catalyst has the advantages of simple preparation method, easy operation and little environmental pollution.
2) The metal particles are uniformly distributed and have high dispersity.
3) The catalyst has excellent conversion rate and selectivity in the application process.
4) The catalyst uses a copper net as a carrier, so that the difficult problem of separation of the catalyst in the separation process after the reaction caused by noble metal loss due to active carbon powdering in the reaction process is avoided.
Detailed description of the preferred embodiments
The embodiments listed in the present invention will be described in detail by way of specific examples, but the scope of the present invention is not limited to the following examples.
The microchannel reactor used in the examples of the present invention was a stainless steel reinforced hybrid microreactor (NYB-MC-1X) from Hengzhou, inc. of Biotechnology.
Example 1
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 2
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 1mm, the mesh size of the copper mesh is 100 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. Putting the copper mesh into palladium ammonia solutionThe solution was then placed in a microwave oven with a microwave power of 300w, a temperature of 100℃and a stirring speed of 5000rpm and a stirring Reynolds number of 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:1.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 3
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.08mm, the mesh size of the copper mesh is 5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment for 30min at 25 ℃, then putting into deionized water, carrying out ultrasonic treatment for 60min at 25 ℃, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment for 30min at 25 ℃, then putting into deionized water, carrying out ultrasonic treatment for 60min at 25 ℃, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is vertical to the metal copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:2 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 4
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 5
Weigh 0.864g PtCl 4 Dissolving with 23-28% ammonia water, and making into 50ml platinum ammonia solution. Putting a copper-iron (1.0 wt%) net (with the diameter of copper wires being 0.05mm and the mesh size of the copper net being 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into a platinum ammonia solution and then put into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequencyThe rate is 3-30GHZ, the duration is 1S, the interval is 1min, and the treatment times are 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.5 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 6
Weigh 0.864g PtCl 4 Dissolving with 23-28% ammonia water, and making into 50ml platinum ammonia solution. Putting a copper-tin (1.0 wt%) net (with the diameter of copper wires being 0.05mm and the mesh size of the copper net being 1 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.7ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 7
Weigh 0.864g PtCl 4 With a concentration of 23-28%After the ammonia water is dissolved, the volume is fixed to form 50ml of platinum ammonia solution. Putting a copper-zinc (1.0 wt%) net (with the diameter of copper wires being 0.05mm and the mesh size of the copper net being 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in a platinum ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 1.0ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 8
Weigh 0.864g PtCl 4 Dissolving with 23-28% ammonia water, and making into 50ml platinum ammonia solution. The copper-nickel (1.0 wt%) net (copper wire diameter 0.05mm, mesh size of copper net 15 um) was put into absolute ethanol and sonicated at 30 ℃ for 40min, then put into deionized water and sonicated at 25 ℃ for 60min, then put into 3mol/L dilute hydrochloric acid and sonicated at 30 ℃ for 40min, then put into deionized water and sonicated at 25 ℃ for 60min, and put into deionized water for standby. The copper mesh is placed in a platinum ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then adjusting the microwave frequency to 30 GHz-300 GHz, the duration to 20s, the interval to 10minAnd (5) carrying out 10 times of treatment. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.5ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 9
Weigh 2.024gNiCl 2 ·6H 2 O, dissolving with 23-28% ammonia water to obtain 50ml nickel ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into nickel ammonia solution and then put into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.2ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 200 ℃. And then detecting the product by using high performance liquid chromatography.
Example 10
Weigh 2.024gNiCl 2 ·6H 2 O, dissolving with 23-28% ammonia water to obtain 50ml nickel ammonia solution. Placing copper mesh (copper wire diameter 0.05mm, mesh size of copper mesh 0.5 um) into absolute ethanol, and standing at 30deg.CSonicating for 40min, then sonicating in deionized water at 25deg.C for 60min, then sonicating in 3mol/L dilute hydrochloric acid at 30deg.C for 40min, then sonicating in deionized water at 25deg.C for 60min, and standing in deionized water. The copper mesh is put into nickel ammonia solution and then put into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 11
Weigh 2.024gNiCl 2 ·6H 2 O, dissolving with 23-28% ammonia water to obtain 50ml nickel ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in nickel ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 300 ℃. And then detecting the product by using high performance liquid chromatography.
Example 12
Weigh 2.024gNiCl 2 ·6H 2 O, dissolving with 23-28% ammonia water to obtain 50ml nickel ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in nickel ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 150 ℃. And then detecting the product by using high performance liquid chromatography.
Example 13
1.294g RuCl was weighed 3 ·3H 2 O, dissolving with 23-28% ammonia water to obtain 50ml ruthenium ammonia solution. Putting copper mesh (copper wire diameter 0.05mm, mesh size of copper mesh 0.5 um) into absolute ethanol, ultrasonic treating at 25deg.C for 30min, then in deionized water for 60min, then in 1mol/L dilute hydrochloric acid for 30min at 25deg.C, and thenUltrasonic treatment is carried out in deionized water at 25 ℃ for 60min, and the solution is put in deionized water for standby. The copper mesh is placed in ruthenium ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 14
1.294g RuCl was weighed 3 ·3H 2 O, dissolving with 23-28% ammonia water to obtain 50ml ruthenium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in ruthenium ammonia solution and then placed in a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 15
1.294g RuCl was weighed 3 ·3H 2 O, dissolving with 23-28% ammonia water to obtain 50ml ruthenium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into rhodium ammonia solution and then put into a microwave oven, the microwave power is 300w, the temperature is adjusted to 150 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 16
1.294g RuCl was weighed 3 ·3H 2 O, dissolving with 23-28% ammonia water to obtain 50ml ruthenium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. Putting the copper mesh into palladium ammonia solution and then putting into a microwave oven,the microwave power was 300w, the temperature was adjusted to 150 ℃, the stirring speed was 5000rpm, and the stirring Reynolds number was adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 10S, interval to 10min, and processing times to 10 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 17
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in palladium ammonia solution and then placed in a microwave oven, the microwave power is 400w, the temperature is adjusted to 100 ℃, the stirring speed is 6000rpm, and the stirring Reynolds number is adjusted to 1500. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Example 18
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is placed in palladium ammonia solution and then placed in a microwave oven, the microwave power is 400w, the temperature is adjusted to 100 ℃, the stirring speed is 6000rpm, and the stirring Reynolds number is adjusted to 1500. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:1 were fed at a flow rate of 0.6ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 300 ℃. And then detecting the product by using high performance liquid chromatography.
Comparative example 1
Weigh 0.847g PdCl 2 Dissolving with ammonia water, and then fixing the volume to obtain 50ml of palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 20 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 20 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting microwave frequency at 3-30GHZ for 1S at intervals of 1min, and treating timesThe number is 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃.
Comparative example 2
Weigh 0.847g PdCl 2 Dissolving with ammonia water, and then fixing the volume to obtain 50ml of palladium ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 40 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 40 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emission direction is parallel to the copper mesh. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃.
Comparative example 3
0.864g PtCl was weighed out 4 Dissolving with ammonia water, and fixing volume to obtain 50ml platinum ammonia solution. Placing copper mesh (copper wire diameter 0.05mm, mesh size of copper mesh 0.5 um) in absolute ethanol, ultrasonic treating at 25deg.C for 30min, and ultrasonic treating in deionized water at 25deg.C for 60minThen the mixture is put into 1mol/L dilute hydrochloric acid to be treated by ultrasonic for 30min at 25 ℃, then put into deionized water to be treated by ultrasonic for 60min at 25 ℃ and put into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emitting direction is perpendicular to the copper net. Setting the microwave frequency at 300MHz-3GHZ, the duration time is 1S, the interval is 1min, and the treatment times are 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 0.5h. Then at N 2 Roasting for 1 hour at 200 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃.
Comparative example 4
0.864g PtCl was weighed out 4 Dissolving with ammonia water, and fixing volume to obtain 50ml platinum ammonia solution. Putting a copper mesh (copper diameter is 0.05mm, mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 30 ℃ for 40min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 30 ℃ for 40min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh is put into palladium ammonia solution and then into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emission direction is parallel to the copper mesh. Setting the microwave frequency at 300MHz-3GHZ, the duration time is 1S, the interval is 1min, and the treatment times are 2 times. Then the microwave frequency is adjusted to 3GHz to 30GHz, the duration is 20s, the interval is 10min, and the treatment is 10 times. After the treatment is completed, the copper mesh temperature is reduced to normal temperature, and then the copper mesh is quickly transferred into deionized water, and the copper mesh is kept stand for 5 hours. Then at N 2 Roasting for 5 hours at 500 ℃ under the atmosphere.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃.
Comparative example 5
1.294g NiCl was weighed 2 ·6H 2 O, dissolving with ammonia water, and then fixing the volume to obtain 50ml of nickel ammonia solution. Putting a copper mesh (the diameter of copper wires is 0.05mm, the mesh size of the copper mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The copper mesh was placed in a nickel ammonia solution and then heated and stirred in a magnetic stirrer at a temperature of 80℃and a stirring speed of 1000rpm. Pouring out the residual liquid after stirring, and placing the solid into a vacuum oven for temperature programming and drying to obtain the catalyst, wherein the temperature programming is as follows: raising the temperature to 50 ℃ from room temperature at 1 ℃/min, and keeping the temperature for 2 hours; then, the temperature was raised from 50℃to 110℃from 1℃per minute and maintained for 2 hours.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃.
Comparative example 6
Weigh 0.847g PdCl 2 Dissolving with 23-28% ammonia water, and making into 50ml palladium ammonia solution. Putting a zinc mesh (the diameter of zinc wires is 0.05mm, the mesh size of the zinc mesh is 0.5 um) into absolute ethyl alcohol, carrying out ultrasonic treatment at 25 ℃ for 30min, then putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, then putting into 1mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25 ℃ for 30min, putting into deionized water, carrying out ultrasonic treatment at 25 ℃ for 60min, and putting into deionized water for standby. The zinc mesh is put into palladium ammonia solution and then put into a microwave oven, the microwave power is 300w, the temperature is adjusted to 100 ℃, the stirring speed is 5000rpm, and the stirring Reynolds number is adjusted to 800. The microwave emission direction is perpendicular to the zinc mesh. Setting microwave frequency to 3-30GHZ, duration to 1S, interval to 1min, and processing times to 2 times. Then the microwave frequency is adjusted to be 30GHz to 300GHz, the duration is 10s, the interval is 1min, and the treatment is carried out for 2 times. After the treatment is completed, after the temperature of the zinc net is reduced to normal temperature, the zinc net is quickly transferred to the zinc netAnd (3) standing in deionized water for 0.5h. Then at N 2 Roasting at 200 ℃ for 1 hour to obtain the catalyst.
Bromoaryl propiophenone and styrene derivatives in a molar ratio of 1:0.1 were fed at a flow rate of 0.1ml/min into a microchannel reactor containing 0.1g of the above catalyst and reacted at 100 ℃. And then detecting the product by using high performance liquid chromatography.
Claims (7)
1. The application of a metal mesh supported metal particle catalyst in the catalytic synthesis of pterostilbene by taking bromoaryl propiophenone shown in a formula (I) and a styrene derivative shown in a formula (II) as raw materials;
the metal mesh supported metal particle catalyst is prepared by a preparation method comprising the following steps:
(1) Preparing a metal impregnating solution: weighing metal precursors with corresponding mass, and then dissolving the metal precursors with 25-28% ammonia water to prepare impregnating solution; the metal precursor is selected from PtCl 4 、NiCl 2 ·6H 2 O、RuCl 3 ·3H 2 At least one of O;
(2) Pretreatment of the wire mesh: putting the wire mesh into absolute ethyl alcohol, carrying out ultrasonic treatment at 25-30 ℃ for 30-40min to remove oil stains on the surface, and then putting into deionized water for ultrasonic treatment to remove the ethyl alcohol; then putting into 3mol/L dilute hydrochloric acid, carrying out ultrasonic treatment at 25-30 ℃ for 30-40min to remove surface oxides, finally adding into deionized water, carrying out ultrasonic treatment to remove acid, and immersing the treated solution into deionized water for standby; the metal wire is made of copper or copper alloy and one or more than two of zinc, iron, tin and nickel;
(3) Load: immersing a wire mesh in an impregnating solution, wherein the impregnating solution is in a violent stirring state, and then applying intermittent microwave treatment to the impregnating solution, wherein the microwave emission direction is perpendicular to the wire mesh, and the intermittent microwave treatment is specifically as follows: setting microwave frequency at 3-30GHZ, wherein each treatment duration is 1-10S, the interval is 1-10min, and the treatment times are 2-10 times; then adjusting the microwave frequency to be 30GHz to 300GHz, wherein the duration of each treatment is 10-20s, the interval is 1-10min, and the treatment times are 2-10 times;
(4) Post-treatment of the catalyst: and (3) cleaning the metal wire mesh loaded in the step (3) by deionized water, drying in the shade, and roasting at 200-500 ℃ for 1-5 hours in an inert atmosphere to obtain the metal particle catalyst loaded on the metal wire mesh.
2. The use according to claim 1, wherein: the application is specifically as follows: the method comprises the steps of taking bromoaryl propiophenone shown in a formula (I) and a styrene derivative shown in a formula (II) as raw materials, wherein the mol ratio of the bromoaryl propiophenone to the styrene derivative is 1:0.1-2, injecting the mixture into a micro-channel reactor containing the metal particle catalyst loaded by a metal wire mesh at a flow rate of 0.1-1ml/min after uniform mixing, and reacting at 100-300 ℃ to obtain pterostilbene.
3. Use according to claim 1 or 2, characterized in that: in step (1), the pH of the impregnation fluid is controlled to be 7-9, wherein the metal content is 0.01-0.04g/ml.
4. Use according to claim 1 or 2, characterized in that: in the step (2), the wire mesh is a mesh woven by wires, the diameter of the wires is 0.01-1mm, and the mesh size of the woven wire mesh is 0.5-100 mu m.
5. Use according to claim 1 or 2, characterized in that: in the step (3), the impregnating solution is placed in a microwave heater for intermittent microwave treatment, the power during microwave treatment is 300-400w, the temperature is 100-150 ℃, the stirring speed is 5000-6000rpm, and the stirring Reynolds number Re=800-1500.
6. Use according to claim 1 or 2, characterized in that: in the step (4), the inert atmosphere is nitrogen or argon.
7. Use according to claim 1 or 2, characterized in that: in the step (4), the step of cleaning the wire mesh loaded in the step (3) by deionized water is to quickly transfer the wire mesh into the deionized water after the temperature of the wire mesh is reduced to normal temperature, and then the wire mesh is kept stand for 0.5 to 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010899639.3A CN112206784B (en) | 2020-08-31 | 2020-08-31 | Application of metal mesh supported metal particle catalyst in catalytic synthesis of pterostilbene |
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| CN202010899639.3A CN112206784B (en) | 2020-08-31 | 2020-08-31 | Application of metal mesh supported metal particle catalyst in catalytic synthesis of pterostilbene |
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| CN108786843A (en) * | 2018-03-27 | 2018-11-13 | 安徽师范大学 | A kind of supported precious metal catalyst, preparation method and applications |
| CN109433124A (en) * | 2018-11-15 | 2019-03-08 | 嘉兴市秀洲区洪合镇中学 | A kind of micro passage reaction of grafted porous palladium/copper catalyst and its preparation and the application method in pterostilbene preparation |
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| CN110368934B (en) * | 2019-08-15 | 2022-08-09 | 安徽元琛环保科技股份有限公司 | Preparation method of wire mesh SCR denitration catalyst and prepared catalyst |
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| CN108786843A (en) * | 2018-03-27 | 2018-11-13 | 安徽师范大学 | A kind of supported precious metal catalyst, preparation method and applications |
| CN109433124A (en) * | 2018-11-15 | 2019-03-08 | 嘉兴市秀洲区洪合镇中学 | A kind of micro passage reaction of grafted porous palladium/copper catalyst and its preparation and the application method in pterostilbene preparation |
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| Title |
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| 尹诗斌 等著.《直接醇类燃料电池催化剂》.《直接醇类燃料电池催化剂》.2013,第14-15页. * |
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