Hydrogen free radical generating device and application thereof

Abstract

The invention discloses a hydrogen free radical generating device and application thereof, the hydrogen free radical generating device comprises a hydrogen free radical generator, a feed port of an anode of the hydrogen free radical generator is connected with a feed port of a flow meter, and a feed port of the flow meter is connected with a discharge port of a first storage chamber; and a discharge hole of the cathode of the hydrogen free radical generator is connected with the reaction raw material chamber. Hydrogen or water or some organic matters are introduced into the anode of the hydrogen free radical generator device, so that the hydrogen or water or some organic matters become hydrogen ions under the action of an anode catalyst and move to the cathode under the action of potential, free radicals are formed at the cathode, and the hydrogen free radical generator device can be applied to various fields by coupling different reaction processes. Therefore, the generation of hydrogen free radicals is quantitatively controlled through current and the supply amount of hydrogen or water or some organic matters, which is difficult to realize by photocatalysis or thermocatalysis.

Description

Technical Field

[0001] This invention relates to the field of hydrogen free radical generation technology, and in particular to a hydrogen free radical generating device and its application. Background Technology

[0002] Free radicals are widely present in nature and human activities, such as atmospheric chemistry, combustion reactions, photochemical reactions, and metabolic processes in living organisms. In biological systems, free radicals play important roles in signal transduction and immune defense. In chemical synthesis, free radicals are commonly used in polymerization reactions (such as free radical polymerization), organic synthesis, and catalytic reactions. Free radicals are highly reactive and often exist only as intermediates in chemical processes; however, their formation is often the rate-determining step in many chemical reactions and an indispensable step in many reactions. Therefore, in some reactions, controlling the quantitative production of free radicals is equivalent to controlling the reaction's progress, which is crucial in industrial production. However, free radicals often annihilate very quickly, making the quantitative production of free radicals a challenging problem.

[0003] Hydrogen radicals require specific conditions to be generated, often necessitating high temperatures or catalysts. Furthermore, their generation rate is generally slow, and the amount produced is difficult to control. Therefore, in reactions involving hydrogen radicals, their formation is often the rate-determining step, influencing the forward progression of the reaction and industrial production. Generating stable hydrogen radicals and coupling them with reactions for practical applications presents significant challenges. Summary of the Invention

[0004] This invention aims to address the problems that current hydrogen radical generation requires specific conditions, often necessitates high temperatures or catalysts, and generally results in slow generation rates and difficult-to-control production amounts, affecting the forward progress of the reaction and making it impossible to quantitatively control the generation of hydrogen radicals in industrial production. The invention provides a mild and universal hydrogen radical generation device and its applications.

[0005] To achieve the above-mentioned technical objectives, the technical solution provided by this invention is as follows: A hydrogen free radical generating device includes a hydrogen free radical generator, wherein the inlet of the anode of the hydrogen free radical generator is connected to the inlet of a flow meter, the inlet of the flow meter is connected to the outlet of a first storage chamber, and the outlet of the cathode of the hydrogen free radical generator is connected to a reaction raw material chamber.

[0006] Furthermore, the feed inlet of the hydrogen radical generator cathode is connected to a circulating pump, which is connected to the reaction material chamber; the discharge outlet of the reaction material chamber is connected to the feed inlet of the second one-way valve and the feed inlet of the fifth one-way valve, respectively.

[0007] Furthermore, the outlet of the second check valve is connected to the inlet of the third storage chamber, and the fifth check valve is connected to the detection system.

[0008] Furthermore, the outlet of the anode of the hydrogen radical generator is connected to the inlet of the first one-way valve, and the outlet of the first one-way valve is connected to the inlet of the second storage chamber.

[0009] Furthermore, the second storage chamber is connected to the first storage chamber, and a fourth check valve is installed between the second storage chamber and the first storage chamber; the second storage chamber is connected to the third storage chamber, and a third check valve is installed between the second storage chamber and the third storage chamber.

[0010] Furthermore, the first storage chamber is used to store hydrogen free radical raw materials, which include any one or a mixture of hydrogen gas, hydrogen isotope gas, water, heavy water, tritium-containing water, methane, ethane, methanol, ethanol, formic acid, acetic acid, ethylene glycol, and glycerol.

[0011] Furthermore, the hydrogen radical generator includes a first end plate, a first insulating layer, a first electrode plate, a first gasket, a membrane electrode, a second gasket, a second bipolar plate, a second electrode plate, a second insulating layer, and a second end plate arranged and connected in sequence.

[0012] Furthermore, the reaction material chamber has a gas-liquid separation function.

[0013] Among them, the gas-liquid separation function of the reaction raw material chamber is achieved in the following two ways: (1) Due to the difference in density between gas and liquid, the gas and liquid materials entering the gas-liquid separator are separated by the natural separation of liquid at the bottom of the separator and natural separation of gas at the top of the separator. (2) Or based on the effect of centrifugal field, the gas and liquid are separated by the strong centrifugal force generated by the high-speed rotating gas-liquid mixture.

[0014] Furthermore, the anolyte catalyst of the membrane electrode includes any one of IrO2, RuO2, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Cd, W, Ir, Pt, Au, Hg, nickel-iron hydroxide, as well as oxides or sulfides of the above metals, or one or more of the above metals and carbon-containing supports.

[0015] Furthermore, the cathode catalyst of the membrane electrode includes any one of Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Cd, W, Ir, Pt, Au, and Hg, as well as oxides, sulfides, or phosphides of the above metals, or one or more of the above metals and carbon-containing supports.

[0016] Furthermore, the proton exchange membrane in the membrane electrode is one or more of a proton exchange membrane having sulfonic acid groups or phosphate groups.

[0017] The present invention also provides an application of the device in hydrogen isotope separation, detritium removal from heavy water, detritium removal from tritium-containing water, mild reduction of inorganic ions, electrochemical hydrogenation of organic matter, and purification of hydrogen-containing gases.

[0018] The present invention has the following beneficial effects: 1. This invention introduces hydrogen gas, water, or some organic matter into the anode of a hydrogen free radical generator, causing it to transform into hydrogen ions under the action of an anode catalyst and then move to the cathode under the influence of electrical potential, forming free radicals at the cathode. Therefore, the generation of hydrogen free radicals can be quantitatively controlled by the current and the supply of raw materials, which is difficult to achieve through photocatalysis or thermocatalysis.

[0019] 2. The hydrogen free radical generator of this invention can be applied in various fields, such as achieving higher separation factors in the field of hydrogen isotope gas separation, and also in the electrochemical hydrogenation of organic matter, detritium removal from heavy water, detritium removal from tritium-containing water, mild reduction of ions in aqueous solutions, and purification of hydrogen-containing gases. Therefore, it has the advantages of low energy consumption, wide application range, mild operating conditions, simple equipment, easy operation, high safety, and environmental friendliness. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the device of the present invention; Figure 2 Schematic diagram of a hydrogen radical generator assembly; Figure 3 A schematic diagram of the components of a hydrogen radical generator; Figure 4 Example 1 shows a schematic diagram of the separation factor for gaseous hydrogen isotopes; Figure 5 Example 2 shows a schematic diagram of the separation factor for gaseous hydrogen isotopes; Figure 6 This is a schematic diagram showing the deuterium removal rate of a hydrogen radical generator in heavy water detritus removal.

[0021] In the picture: Hydrogen radical generator 1, first storage chamber 2, second storage chamber 3, third storage chamber 4, flow meter 5, circulating pump 6, reaction feed chamber 7, first one-way valve 8, second one-way valve 9, third one-way valve 10, fourth one-way valve 11, fifth one-way valve 12, first end plate 13, first insulating layer 14, first electrode plate 15, first bipolar plate 16, first gasket 17, membrane electrode 18, second gasket 19, second bipolar plate 20, second electrode plate 21, second insulating layer 22, second end plate 23 Detailed Implementation

[0022] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0024] like Figure 1 As shown, a hydrogen free radical generating device comprises a first storage chamber 2, the outlet of which is connected to the inlet of a flow meter 5. The outlet of the flow meter 5 is connected to the inlet of the anode of a hydrogen free radical generator 1. The outlet of the anode of the hydrogen free radical generator 1 is connected to the inlet of a first one-way valve 8. The outlet of the first one-way valve 8 is connected to the inlet of a second storage chamber 3. The liquid outlet of the reaction material chamber 7 is connected to the inlet of a circulating pump 6. The outlet of the circulating pump 6 is connected to the inlet of the cathode of the hydrogen free radical generator 1. The outlet of the cathode of the hydrogen free radical generator 1 is connected to the reaction material... The inlet of chamber 7 and the outlet of reaction material chamber 7 are respectively connected to the inlet of the second one-way valve 9 and the inlet of the fifth one-way valve 12. The outlet of the second one-way valve 9 is connected to the inlet of the third storage chamber 4. The outlet of the fifth one-way valve 12 is connected to the detection system. The outlet of the third storage chamber 4 is connected to the inlet of the third one-way valve 10. The outlet of the third one-way valve is connected to the inlet of the second storage chamber 3. The outlet of the second storage chamber 3 is connected to the inlet of the fourth one-way valve 11. The outlet of the fourth one-way valve 11 is connected to the inlet of the first storage chamber 2.

[0025] Specifically, such as Figure 2-3 The diagram shows the structure of a hydrogen free radical generator 1. The hydrogen free radical generator 1 includes a first end plate 13, a first insulating layer 14, a first electrode plate 16, a first gasket 17, a membrane electrode 18, a second gasket 19, a second bipolar plate 20, a second electrode plate 21, a second insulating layer 22, and a second end plate 23, which are arranged and connected in sequence.

[0026] The method for generating hydrogen free radicals using the above-mentioned hydrogen free radical generator includes the following steps: Step 1: Hydrogen, water, or some organic raw materials in the first storage chamber 2 are fed into the anode inlet of the hydrogen free radical generator 1 through a flow meter. Under the action of the anode catalyst and the potential, hydrogen ions are formed. The unreacted raw materials are fed into the second storage chamber 3 for later use under the action of the first one-way valve 8. Step 2: Under the action of the electric field, hydrogen ions move through the proton exchange membrane to the cathode catalyst. The reaction raw material chamber 7 is transported to the cathode of the hydrogen free radical generator 1 by the action of the circulating pump 6 to react with hydrogen free radicals.

[0027] Step 3: The hydrogen gas generated by the unreacted hydrogen radicals enters the reaction raw material chamber 7 along with the raw materials and undergoes gas-liquid separation. The liquid material continues to circulate and participate in the reaction through the circulation pump 6, while the hydrogen gas is output for detection by closing the second one-way valve 9 and opening the fifth one-way valve 12, or by closing the fifth one-way valve 12 and opening the second one-way valve 9 to enter the third storage chamber 4 for storage.

[0028] In addition, for hydrogenation reactions of organic matter or reduction reactions of ions, the hydrogen in the third storage chamber 4 can be transported to the second storage chamber 3 through the action of the third one-way valve 10, and then transported to the first storage chamber 2 through the action of the fourth one-way valve 11 for recycling.

[0029] Example 1 This embodiment illustrates the application of a hydrogen free radical generator in hydrogen isotope separation.

[0030] The Nifion 115 film electrode with Pt / C cathode and Pd / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains a 1:1 hydrogen-deuterium mixture, and the reaction feed chamber contains natural water at 25°C.

[0031] The circulating pump, check valve 8, and check valve 12 were opened respectively, and the flow meter was set to an inlet flow rate of 0.2 L / min. A voltage of 0.1 V was applied to the hydrogen radical generator to operate the system. Testing showed that the separation factor of gaseous hydrogen isotopes in this system was 80, significantly higher than reported by other methods. Figure 4 As shown.

[0032] Example 2 This embodiment illustrates the application of a hydrogen free radical generator in hydrogen isotope separation.

[0033] The Nifion 115 film electrode with Pt / C cathode and Pt / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains a 1:1 hydrogen-deuterium mixture, and the reaction feed chamber contains natural water at 60°C.

[0034] The circulating pump, check valve 8, and check valve 12 were opened respectively, and the flow meter was set to an inlet flow rate of 0.2 L / min. A voltage of 0.1 V was applied to the hydrogen radical generator to operate the system. Testing showed that the separation factor of gaseous hydrogen isotopes in this system was 120, significantly higher than reported by other methods. Figure 5 As shown.

[0035] Example 3 This embodiment demonstrates the application of a hydrogen radical generator in the removal of tritium from heavy water. The tritium removal process is simulated using a deuterium removal simulation.

[0036] The Nifion 115 film electrode with Pt / C cathode and Pt / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains naturally abundant hydrogen, and the reaction raw material chamber contains a mixture of water at 25°C with an H / D ratio of 1:1.

[0037] Open the circulating pump, check valves 8, 9, and 11 respectively, set the flow meter to an inlet flow rate of 0.1 L / min, and apply a 0.1V voltage to the hydrogen radical generator to operate the system. After a period of operation, take a sample of water from the reaction material chamber for testing; the deuterium removal rate reached 99.9%. Figure 6 As shown.

[0038] Example 4: This embodiment illustrates the application of a hydrogen radical generator in the mild reduction of inorganic ions.

[0039] The Nifion 115 film electrode with Pt / C cathode and Pt / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains naturally abundant hydrogen gas, and the reaction raw material chamber contains a room temperature solution of ferric ions.

[0040] The circulating pump, check valves 8, 9, 10, and 11 were opened respectively. The flow meter was set to an inlet flow rate of 0.1 L / min. A voltage of 0.1 V was applied to the hydrogen radical generator to operate the system. After running for a period of time, a 0.1 mol / L potassium thiocyanate solution was added to the aqueous solution in the reaction raw material chamber. The solution did not turn red. However, when a 3% hydrogen peroxide solution was added, the solution turned blood red. This indicates that the device reduced ferric ions to divalent ions.

[0041] Example 5 This embodiment illustrates the application of a hydrogen radical generator in the field of electrochemical hydrogenation of organic compounds.

[0042] The Nifion 115 film electrode with Pt / C cathode and Pd / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains naturally abundant hydrogen gas, and the reaction raw material chamber contains a pyridine aqueous solution at room temperature.

[0043] The circulating pump, check valves 8, 9, 10, and 11 were turned on respectively. The flow meter was set to an inlet flow rate of 0.1 L / min, and a voltage of 1.2 V was applied to the hydrogen radical generator to operate the system. After running for a period of time, the aqueous solution in the reaction raw material chamber was extracted with deuterated chloroform. The results, as detected by 1H NMR spectroscopy, showed that 80% piperidine was generated.

[0044] Example 6: This embodiment illustrates the application of a hydrogen radical generator in the field of electrochemical hydrogenation of organic compounds.

[0045] The Nifion 115 film electrode with Pt / C cathode and Pt / C anode is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains naturally abundant hydrogen, and the reaction raw material chamber contains a room temperature aqueous solution of 3-butyn-1-ol.

[0046] The circulating pump, check valves 8, 9, 10, and 11 were turned on respectively. The flow meter was set to an inlet flow rate of 0.1 L / min, and a voltage of 0.1 V was applied to the hydrogen radical generator to run the system. After running for a period of time, the aqueous solution in the reaction raw material chamber was extracted with deuterated chloroform. The extraction was confirmed by 1H NMR spectroscopy, and 100% n-butanol was produced.

[0047] Example 7: This embodiment illustrates the application of a hydrogen radical generator in the field of electrochemical hydrogenation of organic compounds.

[0048] The Nifion 115 membrane electrode, with IrO2 as the cathode and Pt / C as the anode, is designed according to... Figure 2 Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains naturally abundant water, and the reaction raw material chamber contains a pyridine aqueous solution at room temperature.

[0049] The circulating pump, check valve 8, and check valve 12 were turned on respectively. The flow meter was set to an inlet water flow rate of 0.1 L / min. A voltage of 1.7 V was applied to the hydrogen radical generator to run the system. After running for a period of time, the aqueous solution in the reaction raw material chamber was extracted with deuterated chloroform. The results showed that 95% piperidine was generated by nuclear magnetic resonance spectroscopy.

[0050] Example 8: This embodiment illustrates the application of a hydrogen free radical generator in the field of hydrogen purification.

[0051] The Nifion 115 film electrode with Pt / C cathode and Pt / C anode is designed according to... Figure 2Assemble the hydrogen radical generator as shown, and then proceed with the assembly as follows: Figure 1 The connection is shown. Storage chamber 1 contains hydrogen gas containing other impurities, while the reaction raw material chamber contains water at room temperature.

[0052] Turn on the circulating pump, check valve 8, and check valve 9 respectively, set the flow meter to an inlet flow rate of 0.1 L / min, and apply a voltage of 0.1 V to the hydrogen radical generator to operate the system. After a period of operation, pure hydrogen can be collected in the third storage chamber 4.

[0053] Therefore, this invention has the advantages of low energy consumption, wide application range, mild operating conditions, simple equipment, easy operation, high safety, and environmental friendliness. Based on its principle: a hydrogen-containing substance is introduced into the anode of the hydrogen free radical generator, where it is converted into hydrogen ions under the action of the anode catalyst and moves to the cathode under the influence of potential, forming free radicals at the cathode. The reactant material reacts by contacting the free radicals at the cathode under electrocatalysis. In this way, the generation of hydrogen free radicals can be quantitatively controlled by the current and the supply of raw materials. In some rate-determining steps of free radical-mediated reactions, the rate of free radical generation can be effectively controlled, thereby controlling the reaction rate.

[0054] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0055] The above detailed embodiments are a description of the present invention. It should not be considered that the specific embodiments of the present invention are limited to these descriptions. For those skilled in the art, several simple deductions and substitutions can be made without departing from the concept of the present invention, and all of these should be considered to fall within the protection scope of the present invention.

Claims

1. A hydrogen free radical generating device, characterized in that, It includes a hydrogen radical generator (1), the inlet of the anode of the hydrogen radical generator (1) is connected to the inlet of the flow meter (5), the inlet of the flow meter (5) is connected to the outlet of the first storage chamber (2); the outlet of the cathode of the hydrogen radical generator (1) is connected to the reaction raw material chamber (7).

2. The hydrogen radical generator according to claim 1, characterized in that, The feed inlet of the cathode of the hydrogen radical generator (1) is connected to the circulating pump (6), and the circulating pump (6) is connected to the reaction raw material chamber (7); the discharge outlet of the reaction raw material chamber (7) is connected to the feed inlet of the second check valve (9) and the feed inlet of the fifth check valve (12).

3. The hydrogen free radical generating device according to claim 2, characterized in that, The outlet of the second check valve (9) is connected to the inlet of the third storage chamber (4), and the fifth check valve (12) is connected to the detection system.

4. The hydrogen free radical generating device according to claim 1, characterized in that, The outlet of the anode of the hydrogen radical generator (1) is connected to the inlet of the first check valve (8), and the outlet of the first check valve (8) is connected to the inlet of the second storage chamber (3).

5. The hydrogen free radical generating device according to claim 4, characterized in that, The second storage chamber (3) is connected to the first storage chamber (2), and a fourth check valve (11) is provided between the second storage chamber (3) and the first storage chamber (2); the second storage chamber (3) is connected to the third storage chamber (4), and a third check valve (10) is provided between the second storage chamber (3) and the third storage chamber (4).

6. The hydrogen free radical generating device according to claim 1, characterized in that, The first storage chamber (2) is used to store hydrogen free radical raw materials, which include any one or a mixture of hydrogen gas, hydrogen isotope gas, water, heavy water, tritium-containing water, methane, ethane, methanol, ethanol, formic acid, acetic acid, ethylene glycol, and glycerol.

7. The hydrogen free radical generating device according to claim 1, characterized in that, The hydrogen free radical generator (1) includes a first end plate (13), a first insulating layer (14), a first electrode plate (16), a first gasket (17), a membrane electrode (18), a second gasket (19), a second bipolar plate (20), a second electrode plate (21), a second insulating layer (22), and a second end plate (23) arranged in sequence.

8. The hydrogen free radical generating device according to claim 1, characterized in that, The reaction material chamber (7) has a gas-liquid separation function.

9. The hydrogen free radical generating device according to claim 6, characterized in that, The anolyte catalyst of the membrane electrode includes any one of IrO2, RuO2, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Cd, W, Ir, Pt, Au, Hg, nickel-iron hydroxide, as well as oxides or sulfides of the above metals, or one or more of the above metals and carbon-containing supports.

10. The hydrogen radical generator according to claim 6, characterized in that, The cathode catalyst of the membrane electrode includes any one of Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Cd, W, Ir, Pt, Au, and Hg, as well as oxides, sulfides, or phosphides of the above metals, or one or more of the above metals and carbon-containing supports.

11. The hydrogen radical generator according to claim 6, characterized in that, The proton exchange membrane in the membrane electrode is one or more of the proton exchange membranes having sulfonic acid groups or phosphate groups.

12. An application of the apparatus described in any one of claims 1-10 in hydrogen isotope separation, detritium removal from heavy water, detritium removal from tritium-containing water, mild reduction of inorganic ions, electrochemical hydrogenation of organic matter, and purification of hydrogen-containing gases.

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