CN110961041A - Continuous flow catalytic reactor, method of assembling same and use thereof - Google Patents
Continuous flow catalytic reactor, method of assembling same and use thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
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- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 20
- 230000005684 electric field Effects 0.000 claims abstract description 15
- 238000006345 epimerization reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 15
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 12
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 12
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 12
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- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 6
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- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 claims description 6
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 6
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- 238000011049 filling Methods 0.000 claims description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims description 4
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- 239000011521 glass Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 22
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- 238000006555 catalytic reaction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
- 239000006060 molten glass Substances 0.000 description 2
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101710164401 Omega-aminotransferase Proteins 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Images
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P19/00—Machines for simply fitting together or separating metal parts or objects, or metal and non-metal parts, whether or not involving some deformation; Tools or devices therefor so far as not provided for in other classes
Abstract
The invention discloses a continuous flow catalytic reactor, an assembly method and application thereof. The continuous flow catalytic reactor comprises a reaction container, filler and a charged catalytic component, wherein the filler is packaged in the reaction container, and the catalytic component is fixed on the filler under the action of a direct current electric field. The continuous flow catalytic reactor can be applied to monosaccharide epimerization reaction and other continuous flow reactions. The continuous flow catalytic reactor has the advantages of simple structure, unattended operation, safe and convenient operation and the like, and in the process of applying the continuous flow catalytic reactor to continuous flow reaction, because the catalytic components are fixed by a direct current electric field, the catalytic components cannot flow out along with a product, the separation step of the catalyst is saved, and the utilization efficiency of the catalyst is improved.
Description
Technical Field
The invention relates to a continuous flow catalytic reactor, a method for assembling the same and application thereof, such as application in monosaccharide epimerization reaction.
Background
The traditional kettle type liquid phase reaction solves the problem of the demand of a large amount of chemical products, but has a plurality of defects which are difficult to overcome, such as potential safety hazard, environmental pollution, huge energy consumption, unstable product quality, large floor area, difficult process amplification and the like (chemical development, 2016, 28(6): 829-. Continuous flow reactions solve these problems with their unique mixing patterns, high efficiency of mass and heat transfer, and low solvent requirements. "continuous flow chemistry," otherwise known as "flow chemistry," refers to a technique in which material is delivered by a pump and chemical reactions are carried out in a continuous flow mode. Over the last 20 years, continuous flow reaction technology has become more popular in academia and industry, and its advantages are mainly reflected in: (1) the reactor has small size, rapid mass and heat transfer and easy realization of process enhancement; (2) the parameter control is accurate, the reaction selectivity is good, and the method is particularly suitable for inhibiting series side reactions; (3) the online material quantity is small, the inherent flame retardant property of the micro channel is high, the explosion-proof performance of the device is enhanced due to a small structure, and the operation is safe; (4) continuous operation and high space-time efficiency; (5) easy to realize automatic control, enhance the safety of operation and save labor resources (the journal of Chinese medicine industry, 2017,48 (4): 469-.
Most of the liquid-phase continuous flow reactions are catalytic reactions, and generally, a catalyst and a raw material are premixed and then introduced into a reactor for reaction. If the catalyst is fixed in the reactor, the catalyst separation step can be saved, the loss of the catalyst is reduced, the utilization efficiency of the catalyst is improved, and the service life of the catalyst is prolonged. Commonly used catalyst immobilization methods are physical adsorption and chemical bonding. CN101033192A discloses a continuous flow reaction method for producing mononitrobenzene by nitrating benzene with nitric acid, which comprises the steps of loading metal oxide on an MFI topological structure molecular sieve and pseudo-boehmite by impregnation, and then pressing and forming the mixture into a fixed bed catalyst; biggelaar et al covalently immobilize omega-aminotransferases on 3-aminopropyltriethoxysilane modified porous silica for continuous flow reactions for enantioselective transamination (catalysis, 2017, 7 (54): 1-13);
plasma utilizing ionThe bond immobilizes the molybdate ion on an anion exchange resin for use in an epimerization reaction of glucose to mannose (Applied catalysis, 2008, 334 (1-2): 112-118). Nevertheless, the catalytically active component has a limited binding capacity to the support, and is readily soluble in the liquid medium in continuous flow reactions with loss of activity, resulting in a limited catalyst life.
Disclosure of Invention
The main object of the present invention is to provide a continuous flow catalytic reactor, a method for assembling it and its use, overcoming the drawbacks of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a continuous flow catalytic reactor, which comprises a reaction container and a filler packaged in the reaction container; the method is characterized in that: the continuous flow catalytic reactor also includes a charged catalytic component that is immobilized on the packing under the influence of a direct current electric field.
The embodiment of the invention also provides an assembly method of the continuous flow catalytic reactor, which comprises the following steps:
filling a filler into a reaction vessel, and blocking a liquid flow inlet and a liquid flow outlet of the reaction vessel by using a fiber blocking object, wherein the fiber blocking object can allow liquid flow to pass through but block the filler;
electrically connecting a liquid flow inlet and a liquid flow outlet of the reaction container with a positive electrode or a negative electrode of a direct current power supply, and connecting the negative electrode or the positive electrode of the direct current power supply with the middle part of the filler;
and (3) after the solution containing the charged catalytic component is input into the reaction vessel from the liquid flow inlet, the solution is output from the liquid flow outlet, so that the catalytic component is fixed on the filler.
The embodiment of the invention also provides the application of the continuous flow catalytic reactor in the monosaccharide epimerization reaction.
The embodiment of the invention also provides a monosaccharide epimerization reaction method, which comprises the following steps:
providing said continuous flow catalytic reactor;
electrically connecting said continuous flow catalytic reactor to a dc power source to form said dc electric field; and
heating the reaction vessel to a target temperature, inputting the monosaccharide solution from a liquid flow inlet of the reaction vessel, and collecting the solution containing the target product from a liquid flow outlet of the reaction vessel.
Compared with the prior art, the continuous flow catalytic reactor utilizes the direct current electric field to fix the charged catalytic components on the filler to form the fixed bed catalyst. Inputting the reaction solution at a target temperature, and reacting under the action of the catalytic component to continuously obtain a target product. In the process, the catalytic components are fixed by a direct current field and cannot flow out along with the product, so that the separation step of the catalyst is saved, and the utilization efficiency of the catalyst is improved. By utilizing the reactor, molybdenum oxide quantum dots or molybdate ions and the like can be used as catalytic components to realize the continuous reaction of monosaccharide epimerization. In addition, the application of a dc electric field may promote certain chemical reactions that are sensitive to the electric field.
Drawings
FIG. 1 is a schematic diagram showing the structure of a continuous flow catalytic reactor in example 1 of the present invention.
Detailed Description
In view of the deficiencies of the prior art, the inventors of the present invention have made extensive studies and practice to propose the technical solution of the present invention, as will be explained in more detail below.
The continuous flow catalytic reactor provided by the embodiment of the invention comprises a reaction container, filler and a charged catalytic component, wherein the filler is packaged in the reaction container, and the catalytic component is fixed on the filler under the action of a direct current electric field.
In some embodiments, the reaction vessel is a tubular structure.
In some embodiments, the reaction vessel is made of glass, but may be made of other materials, such as ceramic materials, organic materials, and the like.
In some embodiments, the filler comprises any one of activated carbon, ion exchange resin, or a combination of both, and is not limited thereto.
In some embodiments, the catalytic component comprises quantum dots, which may be, for example, molybdenum oxide quantum dots.
In some embodiments, the catalytic component includes molybdate ions, colloidal iron hydroxide particles, but is not limited thereto.
In some embodiments, the reaction vessel has an inner diameter of 1.5-2 cm, a length of 50-80 cm, and a volume of 100 ml and 200 ml.
In some embodiments, the filler has a particle size of 10 to 50 mesh, and a mass to volume ratio of a total mass of the filler to a volume of the reaction vessel is 50 to 120 g: 100-200 ml.
In some embodiments, the voltage of the DC power source for forming the DC electric field is 5-50 volts.
Embodiments of the present invention also provide a method of assembling any one of the aforementioned continuous flow catalytic reactors, comprising:
filling a filler into a reaction vessel, and blocking a liquid flow inlet and a liquid flow outlet of the reaction vessel by using a fiber blocking object, wherein the fiber blocking object can allow liquid flow to pass through but block the filler;
electrically connecting a liquid flow inlet and a liquid flow outlet of the reaction container with a positive electrode or a negative electrode of a direct current power supply, and connecting the negative electrode or the positive electrode of the direct current power supply with the middle part of the filler;
and (3) after the solution containing the charged catalytic component is input into the reaction vessel from the liquid flow inlet, the solution is output from the liquid flow outlet, so that the catalytic component is fixed on the filler.
In some embodiments, the fibrous plugs include glass wool or quartz wool, and the like, but are not limited thereto.
In some specific embodiments, the filler may be filled into the reaction tube, both ends of the filler are plugged with glass wool or quartz wool, the middle part of the filler is in short connection with the positive electrode or the negative electrode of the direct current power supply, the glass wool or the quartz wool at both ends are in short connection with the opposite electrodes, and after the power is supplied, a certain volume of aqueous solution containing the catalytic component is pumped in from one end of the reaction tube, and pumped out from the other end.
In some embodiments, the voltage of the DC power supply is 5-50 volts.
In some embodiments, the solution comprising the charged catalytic component is a quantum dot solution.
In some embodiments, the concentration of the quantum dot solution is 0.5 to 1 g/l, and the flow rate is 0.2 to 1 ml/min.
In some embodiments, the solution comprising the charged catalytic component is a solution comprising colloidal particles of ferric hydroxide or molybdate ions.
The embodiment of the invention also provides application of any continuous flow catalytic reactor in monosaccharide epimerization reaction.
The embodiment of the invention also provides a monosaccharide epimerization reaction method, which comprises the following steps:
providing any of the foregoing continuous flow catalytic reactors;
electrically connecting said continuous flow catalytic reactor to a dc power source to form said dc electric field; and
heating the reaction vessel to a target temperature, inputting the monosaccharide solution from a liquid flow inlet of the reaction vessel, and collecting the solution containing the target product from a liquid flow outlet of the reaction vessel.
In some embodiments, the target temperature is 60 to 120 ℃.
In some embodiments, the voltage of the DC power supply is 5-50 volts.
In some embodiments, the monosaccharide solution comprises any one or combination of more of glucose, mannose, arabinose, ribose, xylose, and lyxose, and is not limited thereto.
In some embodiments, the monosaccharide solution has a concentration of 1 to 10 wt%.
In some embodiments, the monosaccharide solution has a flow rate of 0.1 to 2 ml/min.
In the continuous flow catalytic reactor provided by the invention, the charged catalytic components are fixed on the filler by using the direct current electric field to form the fixed bed catalyst, so that the loss of the catalyst in the continuous flow reaction can be well inhibited.
The continuous flow catalytic reactor has the advantages of simple structure, unattended operation, safe and convenient operation and the like. The continuous flow catalytic reactor of the invention can be used for carrying out various continuous flow reactions, for example, continuous reactions of monosaccharide epimerization can be realized by using molybdenum oxide quantum dots or molybdic acid ions and the like as catalytic components. In the continuous flow reaction process, a reaction solution is pumped in at a target temperature to react with the catalytic component, so that a target product is continuously obtained. The catalytic components are fixed by a direct current electric field and cannot flow out along with the product, so that the separation step of the catalyst is saved, and the utilization efficiency of the catalyst is improved.
The present invention will be described in detail below with reference to the following drawings and examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1: the structure of a continuous flow catalytic reactor of this example is shown in figure 1. Wherein, the reaction tube 1 is w-shaped and made of glass, the inner diameter is 1.8 cm, the length is 70 cm, and the volume is 178 ml. Filling coconut shell activated carbon filler 2 with the particle size of 12-30 meshes and the mass of 80 g in the reaction tube 1, and respectively packaging two ends of the filler with quartz cotton 3 and 4; openings 7 and 8 are respectively arranged near the liquid inlet 5 and the liquid outlet 6, and graphite electrodes 11 and 12 are sealed and fixed by silicon rubber plugs 9 and 10; two electrodes go deep into the reaction tube 1 and are in short circuit with the quartz cotton 3 and 4 and in short circuit with the negative electrode of the direct current power supply 13; an opening 14 is arranged in the middle of the reaction tube, a silicon rubber plug 15 is used for sealing and fixing a graphite electrode 16, and the electrode extends into the reaction tube 1 to be in short connection with the filler 2 and is in short connection with the positive electrode of the direct current power supply 13.
200 ml of molybdenum oxide quantum dot solution with a concentration of 0.8 g/l were prepared. And (3) switching on a direct current power supply 13, keeping the voltage at 24 volts, pumping the solution into the reaction tube 1 from the liquid inlet at the flow rate of 0.5 ml/min, enabling the solution to flow through the filler 2 and be pumped out from the liquid outlet 6, electrically adsorbing the quantum dots on the filler 2, and completely flowing out the solution to obtain the continuous flow catalytic reactor.
Example 2: the reaction tube 1 of the embodiment 1 is filled with chloride ion exchange resin filler 2, the particle size is 20-50 meshes, the mass is 100 g, two ends of the filler are respectively sealed by glass wool 3 and 4, and the connection mode with a direct current power supply is the same as that of the embodiment 1.
400 ml of molybdic acid solution was prepared, having a concentration of 0.2 g/l. And (3) switching on a direct current power supply 13, keeping the voltage at 10 volts, pumping the solution into the reaction tube 1 from the liquid inlet at the flow rate of 2 ml/min, enabling the solution to flow through the filler 2, pumping the solution out from the liquid outlet 6, and electrically adsorbing molybdic acid ions on the filler 2 to obtain the continuous flow catalytic reactor.
Example 3: coconut shell activated carbon filler 2 with the particle size of 12-30 meshes and the mass of 80 g is filled in the reaction tube 1 in the embodiment 1. The two ends of the filler are respectively encapsulated by glass wool 3 and glass wool 4. The connection direction of the positive electrode and the negative electrode of the direct current power supply is opposite to that of the embodiment 1, the glass wool 3 and 4 at the two ends of the filler are in short circuit with the positive electrode of the power supply 13, and the middle part of the filler is in short circuit with the negative electrode of the power supply 14.
100 ml of iron hydroxide sol having a concentration of 2 g/l were prepared. And (3) switching on a direct current power supply 13, keeping the voltage at 50 volts, pumping the sol into the reaction tube 1 from the liquid inlet at the flow rate of 0.2 ml/min, enabling the sol to flow through the filler 2 and be pumped out from the liquid outlet 6, and electrically adsorbing the ferric hydroxide colloid particles on the filler 2 to obtain the continuous flow catalytic reactor.
Example 4: heating the reactor of example 1 in a water bath manner, immersing the reaction tube 1 in a water bath kettle, keeping the liquid inlet 5 and the liquid outlet 6 above the water surface, heating to 80 ℃, turning on a direct current power supply 13, and maintaining the voltage at 24 volts; pumping glucose solution from a liquid inlet 5, wherein the mass concentration of the glucose solution is 3%, and the flow rate is 0.3 ml/min; the solution containing the target product mannose is collected from the liquid outlet 6. The reaction was continued for 7 days, and the yield of mannose was maintained at about 23%.
Example 5: heating the reactor of example 1 in an oil bath, immersing the reaction tube 1 in an oil bath pan, keeping the liquid inlet 5 and the liquid outlet 6 above the oil level, heating to 90 ℃, turning on the direct current power supply 13, and maintaining the voltage at 24 volts; pumping a mannose solution from a liquid inlet 5, wherein the mass concentration of the mannose solution is 1 percent, and the flow rate is 0.1 ml/min; the solution containing the target product glucose is collected from the liquid outlet 6. The reaction was continued for 7 days, and the yield of glucose was maintained at about 60%.
Example 6: heating the reactor of example 2 in an oil bath, immersing the reaction tube 1 in an oil bath pan, with the liquid inlet 5 and the liquid outlet 6 kept above the oil level, heating to 100 ℃, turning on the dc power supply 13, and maintaining the voltage at 40 volts; pumping arabinose solution into the liquid inlet 5, wherein the mass concentration of the arabinose solution is 5 percent, and the flow rate is 1 ml/min; the solution containing ribose as the target product is collected from the liquid outlet 6. The reaction was continued for 3 days, and the yield of ribose was maintained at about 35%.
Example 7: heating the reactor of example 2 in an oil bath, immersing the reaction tube 1 in an oil bath pan, keeping the liquid inlet 5 and the liquid outlet 6 above the water surface, heating to 100 ℃, turning on the direct current power supply 13, and maintaining the voltage at 40 volts; pumping a ribose solution from a liquid inlet 5, wherein the mass concentration of the ribose solution is 5 percent, and the flow rate is 1 ml/min; and collecting the solution containing the target product arabinose from a liquid outlet 6. The reaction was continued for 3 days, and the yield of arabinose was maintained at about 62%.
Example 8: heating the reactor of example 1 in an oil bath, immersing the reaction tube 1 in an oil bath pan, keeping the liquid inlet 5 and the liquid outlet 6 above the oil level, heating to 110 ℃, turning on the direct current power supply 13, and maintaining the voltage at 10 volts; pumping a xylose solution from a liquid inlet 5, wherein the mass concentration of the xylose solution is 10 percent, and the flow rate is 2 ml/min; collecting the solution containing target product lyxose from the liquid outlet 6. The reaction is continued for 3 days, and the yield of the lyxose is maintained at about 30 percent.
Example 9: heating the reactor of example 1 in an oil bath, immersing the reaction tube 1 in an oil bath pan, keeping the liquid inlet 5 and the liquid outlet 6 above the oil level, heating to 120 ℃, turning on the direct current power supply 13, and maintaining the voltage at 10 volts; pumping lyxose solution into the liquid inlet 5, wherein the mass concentration of the lyxose solution is 10%, and the flow rate is 2 ml/min; the solution containing the target product xylose is collected from the liquid outlet 6. The reaction was continued for 3 days, and the yield of xylose was maintained at about 52%.
Comparative example 1: dissolving 250 g of sodium molybdate in water, diluting to 500 ml of constant volume, adding 303 g of chloride ion exchange resin, stirring at room temperature for 16 hours, adding 5 drops of 33% hydrogen peroxide solution, washing the filtered solid with water for 5 times, sucking to dryness, dropwise adding 1 mol/L hydrochloric acid to adjust the pH value to 3.5, and filtering to obtain the wet catalyst. The wet catalyst was charged into a 25 ml electrically heatable glass tube with a thermocouple and encapsulated with glass wool at the molten glass to give a continuous flow reactor. A glucose solution (50% by mass, pH 3.5 adjusted with 1 mol/l hydrochloric acid) was pumped at 90 ℃ at a flow rate of 50 ml/h for the epimerization continuous flow reaction. The initial yield of mannose was around 22% and after 3 days of reaction, the yield dropped to 3% due to molybdenum loss. (reference: applied catalysis, 2008, 334 (1-2): 112-118).
Comparative example 2: 44.14 g of molybdic acid was dissolved in water at 70 ℃ to a constant volume of 500 ml, 50 g of a chloride ion exchange resin was added, stirring was carried out at 40 ℃ for 24 hours, 1 mol/l hydrochloric acid was added dropwise to adjust the pH to 3.5, and then the filtered solid was washed with water 5 times to obtain a wet catalyst. The wet catalyst was charged into a 25 ml electrically heatable glass tube with a thermocouple and encapsulated with glass wool at the molten glass to give a continuous flow reactor. A glucose solution (50% by mass, pH 3.5 adjusted with 1 mol/l hydrochloric acid) was pumped at 90 ℃ at a flow rate of 50 ml/h for the epimerization continuous flow reaction. The initial yield of mannose was around 27%, and after 7 days of reaction, the yield dropped to around 23% due to molybdenum loss. After reaction 33, the yield decreased to about 12%, and about 1/3% of molybdenum was lost (ref: Applied catalysis, 2008, 334 (1-2): 112-.
In addition, the present inventors have also conducted experiments with other raw materials and conditions, etc. listed in the present specification, in the manner of examples 1 to 9, and also successfully applied to a continuous flow reaction using the continuous flow catalytic reactor of the present invention.
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A continuous flow catalytic reactor comprising a reaction vessel and a packing enclosed within the reaction vessel; the method is characterized in that: the continuous flow catalytic reactor also includes a charged catalytic component that is immobilized on the packing under the influence of a direct current electric field.
2. The continuous-flow catalytic reactor of claim 1, wherein: the reaction vessel is of a tubular structure; and/or, the reaction vessel is made of glass; and/or the filler comprises any one or the combination of two of active carbon and ion exchange resin; and/or, the catalytic component comprises quantum dots, the quantum dots comprising molybdenum oxide quantum dots; alternatively, the catalytic component comprises molybdate ions or iron hydroxide colloidal particles.
3. The continuous-flow catalytic reactor of claim 2, wherein: the inner diameter of the reaction container is 1.5-2 cm, the length is 50-80 cm, and the volume is 100 ml and 200 ml; and/or the filler has a particle size of 10-50 meshes, and the mass-to-volume ratio of the total mass of the filler to the volume of the reaction vessel is 50-120 g: 100-200 ml.
4. The continuous-flow catalytic reactor of claim 1, wherein: the voltage of a direct current power supply for forming the direct current electric field is 5-50 volts.
5. The method of assembling the continuous-flow catalytic reactor of any of claims 1-4, comprising:
filling a filler into a reaction vessel, and blocking a liquid flow inlet and a liquid flow outlet of the reaction vessel by using a fiber blocking object, wherein the fiber blocking object can allow liquid flow to pass through but block the filler;
electrically connecting a liquid flow inlet and a liquid flow outlet of the reaction container with a positive electrode or a negative electrode of a direct current power supply, and connecting the negative electrode or the positive electrode of the direct current power supply with the middle part of the filler;
and (3) after the solution containing the charged catalytic component is input into the reaction vessel from the liquid flow inlet, the solution is output from the liquid flow outlet, so that the catalytic component is fixed on the filler.
6. The method of assembly of claim 5, wherein: the fiber blocking object comprises glass wool or quartz wool.
7. The method of assembly of claim 5, wherein: the voltage of the direct current power supply is 5-50 volts; and/or the solution containing the charged catalytic component is a quantum dot solution, the concentration of the quantum dot solution is 0.5-1 g/L, and the flow rate is 0.2-1 ml/min; alternatively, the solution comprising the charged catalytic component is a solution comprising molybdate ions or iron hydroxide colloidal particles.
8. Use of the continuous flow catalytic reactor according to any of claims 1-4 for the epimerisation of monosaccharides.
9. A method for epimerization of a monosaccharide, comprising:
providing a continuous-flow catalytic reactor according to any of claims 1-4;
electrically connecting said continuous flow catalytic reactor to a dc power source to form said dc electric field; and
heating the reaction vessel to a target temperature, inputting the monosaccharide solution from a liquid flow inlet of the reaction vessel, and collecting the solution containing the target product from a liquid flow outlet of the reaction vessel.
10. The process for epimerization of monosaccharides as claimed in claim 9, wherein: the target temperature is 60-120 ℃; and/or the voltage of the direct current power supply is 5-50 volts; and/or, the monosaccharide solution comprises any one or combination of more of glucose, mannose, arabinose, ribose, xylose, and lyxose; and/or the concentration of the monosaccharide solution is 1-10 wt%; and/or the flow rate of the monosaccharide solution is 0.1-2 ml/min.
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