Device and method for preparing deuterated acid by bipolar membrane device

Abstract

The invention discloses a device for preparing deuterated acid by using a bipolar membrane device. The device comprises a bipolar membrane stack, a power supply and a peristaltic pump, the bipolar membrane stack consists of a bipolar membrane, a cation exchange membrane, an anion exchange membrane and positive and negative electrode plates on two sides, which are alternately arranged and separated by plastic grids; the positive and negative electrode plates are respectively connected with the positive and negative electrodes of the power supply, and positive and negative electrode chambers are respectively formed between the positive and negative electrode plates and the bipolar membrane; a bipolar membrane, an anion exchange membrane, a cation exchange membrane and a bipolar membrane are sequentially arranged between the anode and the cathode to form a repeating unit, and an acid chamber, a salt chamber and an alkali chamber are sequentially formed; the anode chamber is connected with the cathode chamber, and solutions in the feed liquid chamber, the acid chamber, the alkali chamber, the anode chamber and the cathode chamber form circular flow between the bipolar membrane stack and the storage tank connected with the bipolar membrane stack under the driving of the peristaltic pump with a pole chamber liquid storage tank containing strong electrolyte. The device avoids adverse conditions such as violent reaction or redundant process and the like while phase change is not involved, and realizes green, environment-friendly, mild and controllable preparation of deuterated acid.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochemical synthesis, and more particularly to a device and method for preparing deuterated acid using a bipolar membrane device. Background Art

[0002] Deuterated acids and bases are the foundation of deuterated reagents and are widely used in the synthesis of deuterated drugs, the modification of optoelectronic materials, and basic scientific research, including isotope tracing, nuclear magnetic resonance characterization, and nuclear reactions. As important raw materials for converting heavy water into downstream products, the current preparation process for deuterated acids and bases is complex and extremely environmentally unfriendly. For example, the current process for deuterated sulfuric acid (D2SO4) is similar to that for sulfuric acid (H2SO4). SO2, prepared by heating pyrite with oxygen, is oxidized to SO3, which is then brought into contact with heavy water and concentrated in an absorption tower. Currently, there is a lack of mature and stable processes for converting heavy water into deuterated acids in a green and efficient manner.

[0003] By dissociation of heavy water in the bipolar membrane interface layer (D2O→OD - +D + ), provides deuterium ions and deuterium oxide ions in situ under mild conditions, and combines with other ion exchange membranes to directly convert salts into corresponding deuterated acids and bases. Under reverse voltage, heavy water molecules are split into deuterium ions (D + ) and deuterium oxide ions (OD - ), it is possible to directly realize a one-step method to convert inorganic salts into corresponding deuterated acids and bases. No other chemical reagents are consumed in the process, and no by-products are generated. Therefore, the use of bipolar membrane devices to prepare deuterated acids and bases has good industrial prospects. Currently, there are few patents for the preparation of deuterated acids and bases. For example, Chinese patent CN115784159B mixes phenyltrichlorosilane and a dispersant in a reactor, and adds heavy water dropwise to generate deuterium chloride gas. This process has the advantage of large-scale preparation, but the introduction of a dispersant in the synthesis process consumes organic solvents. In addition, Chinese patent CN114751380A directly reacts heavy water with phosphorus trichloride to prepare deuterium chloride gas, which is then absorbed by heavy water to prepare deuterated hydrochloric acid. The process flow is relatively cumbersome and involves violent phase reactions. As for other deuterated acid and base preparation processes, they are complex and diverse, and a universal device and process are urgently needed. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide an apparatus and method for preparing deuterated acids using a bipolar membrane device. The bipolar membrane device is used to prepare deuterated acids, which avoids adverse conditions such as violent reactions or complicated processes without involving phase changes, thereby achieving a green, environmentally friendly, mild and controllable preparation of deuterated acids.

[0005] The present invention provides a device for preparing deuterated acid using a bipolar membrane device, comprising:

[0006] Bipolar membrane stack, power supply, peristaltic pump;

[0007] The bipolar membrane stack is composed of a bipolar membrane, a cation exchange membrane, an anion exchange membrane that are alternately arranged and separated by a plastic grid, and cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative poles of the power supply, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; the arrangement order between the anode and the cathode of the bipolar membrane stack is bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane to form a repeating unit, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber, and is connected to the cathode chamber liquid storage tank containing a strong electrolyte. Under the drive of a peristaltic pump, the solutions in the liquid chamber, acid chamber, alkali chamber, anode chamber and cathode chamber form a circulation flow between the bipolar membrane stack and the connected storage tank.

[0008] Preferably, the cathode and anode electrode plates are made of titanium coated with ruthenium.

[0009] Preferably, the bipolar membrane in the bipolar membrane stack is a special ion exchange membrane with a sandwich structure consisting of a cation membrane layer, a catalyst layer, and a cathodic membrane layer. When assembled, the cation membrane layer faces the cathode and the cathodic membrane layer faces the anode.

[0010] The present invention also provides a method for preparing deuterated acid using a bipolar membrane device, comprising the following steps:

[0011] The device for preparing deuterated acid using the bipolar membrane device described in the above technical solution dissociates heavy water molecules into deuterium ions and deuteroxide ions under the action of an electric field, and then combines the deuterium ions with anions passing through the anion exchange membrane to form deuterated acid in the acid chamber.

[0012] Preferably, all ion exchange membranes in the apparatus for preparing deuterated acid using a bipolar membrane device are first subjected to a system transition; the system transition is specifically performed as follows:

[0013] Transition from water system to heavy water system.

[0014] Preferably, the process of transitioning from the water system to the heavy water system is specifically as follows:

[0015] The ion exchange membrane was sequentially soaked in 20% heavy water, 40% heavy water, 60% heavy water, and 80% heavy water for 1 to 3 hours each, and then soaked in 100% heavy water for 20 to 30 hours.

[0016] Preferably, the apparatus for preparing deuterated acid using a bipolar membrane device is placed in a glove box during operation to prevent water molecules in the air from dissolving into the prepared deuterated acid.

[0017] Preferably, the solvent in the system is heavy water.

[0018] Preferably, the anion is provided by a strong electrolyte; the strong electrolyte is selected from one or more of K2SO4, Na2SO4, Li2SO4, KNO3, NaNO3, LiNO3, KCl, NaCl, LiCl, LiF, NaF, and KF.

[0019] Preferably, the flow rate of the liquid in each chamber is 1 cm / s to 10 cm / s, and the current density is 40 mA / cm 2 ~120mA / cm 2 , the current is set to 1A~1.2A.

[0020] The invention provides a device for preparing deuterated acid using a bipolar membrane device, comprising: a bipolar membrane stack, a power supply, and a peristaltic pump; the bipolar membrane stack comprises a bipolar membrane, a cation exchange membrane, and an anion exchange membrane that are alternately arranged and separated by a plastic grid, as well as cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative poles of the power supply, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; a repeating unit is arranged from the anode to the cathode of the bipolar membrane stack in the order of bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber and is connected to a chamber liquid storage tank containing a strong electrolyte, and under the drive of the peristaltic pump, solutions in the feed liquid chamber, acid chamber, alkali chamber, anode chamber, and cathode chamber circulate between the bipolar membrane stack and the connected storage tanks. Compared with the prior art, the apparatus for preparing deuterated acid using a bipolar membrane device provided by the present invention adopts a specific structure and connection relationship to achieve better overall interaction. While not involving phase change, it avoids unfavorable conditions such as violent reaction or complicated process, thereby achieving green, environmentally friendly, mild and controllable preparation of deuterated acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the bipolar membrane device in Examples 1 and 2 of the present invention;

[0022] Figure 2 Schematic diagram of the concentration changes of potassium deuterium oxide and deuterated sulfuric acid in Example 1 of the present invention;

[0023] Figure 3 Schematic diagram of changes in concentrations of potassium deuterium oxide and deuterated sulfuric acid in Example 2 of the present invention;

[0024] Figure 4 Schematic diagram of a bipolar membrane device in Example 3 of the present invention;

[0025] Figure 5 Schematic diagram of the concentration changes of deuterated nitric acid and sodium deuteride in Example 3 of the present invention;

[0026] Figure 6Schematic diagram of a bipolar membrane device in Example 4 of the present invention;

[0027] Figure 7 Schematic diagram of changes in concentrations of lithium deuterium oxide and deuterated hydrochloric acid in Example 4 of the present invention;

[0028] Figure 8 Schematic diagram of a bipolar membrane device in Example 5 of the present invention;

[0029] Figure 9 Schematic diagram of the change in deuterated fluoride concentration in Example 5 of the present invention. DETAILED DESCRIPTION

[0030] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] The present invention provides a device for preparing deuterated acid using a bipolar membrane device, comprising:

[0032] Bipolar membrane stack, power supply, peristaltic pump;

[0033] The bipolar membrane stack is composed of a bipolar membrane, a cation exchange membrane, an anion exchange membrane that are alternately arranged and separated by a plastic grid, and cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative poles of the power supply, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; the arrangement order between the anode and the cathode of the bipolar membrane stack is bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane to form a repeating unit, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber, and is connected to the cathode chamber liquid storage tank containing a strong electrolyte. Under the drive of a peristaltic pump, the solutions in the liquid chamber, acid chamber, alkali chamber, anode chamber and cathode chamber form a circulation flow between the bipolar membrane stack and the connected storage tank.

[0034] The present invention provides an apparatus and method for preparing deuterated acids using a bipolar membrane device. The apparatus and method utilize the dissociation characteristics of heavy water in the middle layer of the bipolar membrane, adopt a bipolar membrane device with a BP-AC configuration, and employ a system in which all solvents are heavy water solutions. A strong electrolyte is introduced as a raw material into a feed liquid chamber of the bipolar membrane device. Deuterium ions and deuterium oxide ions dissociated from the heavy water in the middle layer of the bipolar membrane react with acid radical ions passing through an anion exchange membrane along the direction of the electric field to form deuterated acids. The apparatus and method utilize a saturated feed method and a high current density to prepare high-concentration deuterated acids. The apparatus and method are simple to operate, environmentally friendly, and can be used to prepare a variety of deuterated acids.

[0035] In the present invention, the apparatus for preparing deuterated acid by the bipolar membrane device (see Figure 1 As shown) includes a bipolar membrane stack, a power supply, and a peristaltic pump, and preferably consists of a bipolar membrane stack, a power supply, and a peristaltic pump.

[0036] In the present invention, the bipolar membrane stack is composed of a bipolar membrane, a cation exchange membrane, an anion exchange membrane, which are alternately arranged and separated by a plastic grid, and cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative poles of the power supply, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; the arrangement order between the anode and the cathode of the bipolar membrane stack is bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane to form a repeating unit, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber, and is connected to the cathode chamber liquid storage tank containing a strong electrolyte. Under the drive of a peristaltic pump, the solutions in the liquid chamber, acid chamber, alkali chamber, anode chamber and cathode chamber form a circulation flow between the bipolar membrane stack and the connected storage tank.

[0037] In the present invention, the material of the cathode and anode plates is preferably titanium coated with ruthenium.

[0038] In the present invention, the bipolar membrane in the bipolar membrane stack is preferably a special ion exchange membrane with a sandwich structure consisting of a cation membrane layer, a catalyst layer, and a cathodic membrane layer. When assembled, the cation membrane layer faces the cathode and the cathodic membrane layer faces the anode.

[0039] The present invention also provides a method for preparing deuterated acid using a bipolar membrane device, comprising the following steps:

[0040] The device for preparing deuterated acid using the bipolar membrane device described in the above technical solution dissociates heavy water molecules into deuterium ions and deuteroxide ions under the action of an electric field, and then combines the deuterium ions with anions passing through the anion exchange membrane to form deuterated acid in the acid chamber.

[0041] In the present invention, all ion exchange membranes in the apparatus for preparing deuterated acid using a bipolar membrane device are preferably first subjected to a system transition; the system transition is preferably carried out in the following manner:

[0042] Transition from water system to heavy water system.

[0043] In the present invention, the process of transitioning from the water system to the heavy water system is preferably as follows:

[0044] Soak the ion exchange membrane in 20% heavy water, 40% heavy water, 60% heavy water, and 80% heavy water for 1 to 3 hours each, and then soak it in 100% heavy water for 20 to 30 hours;

[0045] More preferably:

[0046] The ion exchange membrane was sequentially soaked in 20% heavy water, 40% heavy water, 60% heavy water, and 80% heavy water for 2 hours each, and then soaked in 100% heavy water for 24 hours.

[0047] In the present invention, the apparatus for preparing deuterated acid using a bipolar membrane device is preferably placed in a glove box during operation to prevent water molecules in the air from dissolving into the prepared deuterated acid.

[0048] In the present invention, in the method for preparing deuterated acid using a bipolar membrane device, the solvent in the system is heavy water.

[0049] In the present invention, the anion is preferably provided by a strong electrolyte; the strong electrolyte is preferably selected from one or more of K2SO4, Na2SO4, Li2SO4, KNO3, NaNO3, LiNO3, KCl, NaCl, LiCl, LiF, NaF, and KF. The present invention has no particular limitation on the source of the strong electrolyte; commercially available products known to those skilled in the art can be used.

[0050] In a preferred embodiment of the present invention, the electrode chamber uses K2SO4 with a concentration of 0.3 mol as a strong electrolyte. The present invention has no special restrictions on its dosage, and any volume can be used, specifically 200 mL; the liquid chamber is a salt solution to be converted (K2SO4, Na2SO4, Li2SO4, etc.), and the present invention has no special restrictions on its concentration; the initial solution in the acid-base chamber is heavy water, and the present invention has no special restrictions on the chamber volume, and different volumes of heavy water solutions can be set according to the expected deuterated acid concentration.

[0051] In the present invention, ion injection is used to increase the concentration of the prepared deuterated acid, specifically, the salt solution in the feed chamber is always kept in a supersaturated state; at the same time, a peristaltic pump is used to circulate the corresponding solution of each chamber between the membrane stack and the liquid storage tank, and circulate inside the membrane stack for more than 10 minutes to eliminate the influence of bubbles in the membrane stack on the experiment, and then the power is turned on. When the concentration of the acid chamber no longer increases, the experiment is stopped; the flow rate of the liquid in each chamber is preferably 1 cm / s to 10 cm / s, more preferably 3 cm / s to 5 cm / s, and the constant current operation is performed, and the current density is preferably 40 mA / cm 2 ~120mA / cm 2 , more preferably 50 mA / cm 2 ~100mA / cm 2 The current setting is preferably 1A to 1.2A, more preferably 1.1A.

[0052] The present invention provides an apparatus and method for preparing deuterated acids using a bipolar membrane device, which can achieve green, environmentally friendly, mild and controllable preparation of deuterated acids; and can also achieve the preparation of multiple deuterated acids such as deuterated hydrochloric acid, deuterated sulfuric acid, deuterium fluoride, deuterated phosphoric acid, etc.; compared with the prior art, the present invention has the following beneficial effects: the present invention is simple to operate, mild conditions, does not involve a phase inversion process, has low energy consumption, has a high membrane stack integration, is flexible to use, can meet the requirements of online deuterated acid preparation, and only consumes inorganic salts and heavy water, without the need to introduce other toxic chemicals during the process, which is environmentally friendly; based on the present invention, multiple deuterated acids are prepared respectively, and the preparation of high-concentration deuterated acids is achieved by adopting saturated feed and high current density, which can meet multiple process requirements; therefore, preparing deuterated acids using a bipolar membrane device is a green, environmentally friendly and economical production method with important industrial application prospects.

[0053] The invention provides a device for preparing deuterated acid using a bipolar membrane device, comprising: a bipolar membrane stack, a power supply, and a peristaltic pump; the bipolar membrane stack comprises a bipolar membrane, a cation exchange membrane, and an anion exchange membrane that are alternately arranged and separated by a plastic grid, as well as cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative poles of the power supply, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; a repeating unit is arranged from the anode to the cathode of the bipolar membrane stack in the order of bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber and is connected to a chamber liquid storage tank containing a strong electrolyte, and under the drive of the peristaltic pump, solutions in the feed liquid chamber, acid chamber, alkali chamber, anode chamber, and cathode chamber circulate between the bipolar membrane stack and the connected storage tanks. Compared with the prior art, the apparatus for preparing deuterated acid using a bipolar membrane device provided by the present invention adopts a specific structure and connection relationship to achieve better overall interaction. While not involving phase change, it avoids unfavorable conditions such as violent reaction or complicated process, thereby achieving green, environmentally friendly, mild and controllable preparation of deuterated acid.

[0054] To further illustrate the present invention, the following examples are provided for detailed description. In the following examples of the present invention, the anode and cathode plates on both sides of the membrane stack are made of corrosion-resistant titanium coated with ruthenium, the separator is made of acrylic plate with a thickness of 3 mm, the bipolar membrane used in the membrane stack is BP-1E sold by Astom, Japan, the anion exchange membrane is AMX sold by Astom, Japan, and the cation exchange membrane is CMX sold by Astom, Japan, and the effective area of ​​a single membrane is 22 cm 2; In order to ensure that the entire system operates in an anhydrous system, all ion exchange membranes to be used need to be transitioned from the water system to the heavy water system. The specific process is to soak the ion exchange membrane in 20% heavy water, 40% heavy water, 60% heavy water, and 80% heavy water for 2 hours each, and then soak it in 100% heavy water solution for 24 hours. At the same time, this experimental process needs to be isolated from the air and operated in a glove box.

[0055] The method of preparing deuterated acid using the above-mentioned bipolar membrane device of the present invention mainly comprises:

[0056] First, 200 mL of 0.3 mol / L inorganic salt heavy water solution was introduced into the feed liquid chamber of the bipolar membrane electrochemical reactor, 100 mL of heavy water solution was introduced into the acid and alkali chambers respectively, and 0.3 mol / L K2SO4 solution was introduced into the electrode chamber. The feed liquids in each compartment were then circulated by a peristaltic pump for 10 to 20 minutes to remove the air in the bipolar membrane stack as much as possible. Then, a DC power supply (current density of 10 mA / cm2) connected to the anode and cathode of the membrane stack was turned on. 2 ~120mA / cm 2 ), under the action of the electric field, heavy water dissociates at the interface layer of the bipolar membrane to produce deuterium oxide ions (OD - ) combines with metal cations passing through the cation exchange membrane to form deuterated bases, and the deuterium ions (D + ) combines with anions passing through the anion exchange membrane to form deuterated acids in the acid chamber; therefore, the device can continuously convert inorganic salts into corresponding deuterated acids and bases, and the flow rate of the liquid in each chamber is controlled by a peristaltic pump to be 3cm / s to 10cm / s.

[0057] Example 1

[0058] Example 1 uses Figure 1 The bipolar membrane device was designed with the solutions between the electrode compartments connected in series. A 200 mL solution of 0.3 mol / L potassium sulfate was introduced into the feed compartment. 200 mL of 0.3 mol / L potassium sulfate solution was introduced into the feed compartment, and 100 mL of heavy water was introduced into each of the acid and base compartments. During the experiment, the flow rate of the liquid in each compartment was 3 cm / s, and the current density was 50 mA / cm2. 2 , the current is set to 1.1A.

[0059] The experiment was stopped when the conductivity of the liquid chamber fell below 10mS / cm. The concentration of deuterated sulfuric acid obtained in the acid chamber was 0.64mol / L, and the concentration of potassium deuteride was 1.34mol / L. The energy consumption for preparing deuterated sulfuric acid was 49.65kWh / kg, and the energy consumption for preparing potassium deuteride was 51.75kWh / kg. It should be noted that this device is laboratory-sized, and the energy consumption is expected to be reduced to 2kWh / kg (KOH) for industrial use through process optimization. Figure 2 shown.

[0060] Example 2

[0061] The apparatus and process steps for preparing potassium deuterium oxide / deuterated sulfuric acid in Example 2 are the same as those in Example 1, except that the feed to the liquid chamber is always kept at a saturated concentration, and the current density is set to 100 mA / cm 2 Finally, 2.75 mol / L of deuterated sulfuric acid D2SO4 and 5.82 mol / L of potassium deuteride KOD were obtained, with energy consumption of 11.46 kWh / kg and 8.61 kWh / kg respectively. Figure 3 shown.

[0062] This embodiment adopts saturated feed and high current density to achieve the preparation of high-concentration deuterated acid.

[0063] Example 3

[0064] Example 3 uses Figure 4 The bipolar membrane device was designed with the solutions between the electrode compartments connected in series. 200 mL of 0.3 mol / L potassium sulfate solution was introduced into the feed compartment, 200 mL of a deuterated water solution containing 0.6 mol / L sodium nitrate was introduced into the feed compartment, and 100 mL of deuterated water was introduced into each of the acid and base compartments. During the experiment, the flow rate of the liquid in each compartment was 3 cm / s, and the current density was 50 mA / cm2. 2 , the current is set to 1.1A.

[0065] The experiment was stopped when the conductivity of the liquid chamber was lower than 10mS / cm. The concentration of deuterated nitric acid DNO3 in the acid chamber was 1.43mol / L, and the concentration of sodium deuteride NaOD was 1.43mol / L. The energy consumption for preparing deuterated nitric acid was 12.37kWh / kg, and the energy consumption for preparing potassium deuteride was 16.57kWh / kg. Figure 5 shown.

[0066] Example 4

[0067] Example 4 uses Figure 6 The bipolar membrane device was designed with the solutions between the electrode compartments connected in series. 200 mL of 0.3 mol / L potassium sulfate solution was introduced into the feed compartment. 200 mL of a deuterated water solution containing 0.6 mol / L lithium chloride was introduced into the feed compartment. 100 mL of deuterated water was introduced into each of the acid and base compartments. During the experiment, the flow rate of the liquid in each compartment was 3 cm / s, and the current density was 50 mA / cm. 2 , the current is set to 1.1A.

[0068] The experiment was stopped when the conductivity of the liquid chamber was lower than 10mS / cm. The concentration of deuterated hydrochloric acid DCl obtained in the acid chamber was 1.48mol / L, and the concentration of lithium deuteride LiOD was 1.20mol / L. The energy consumption for preparing deuterated hydrochloric acid was 19.16kWh / kg, and the energy consumption for preparing potassium deuteride was 27.86kWh / kg. Figure 7 shown.

[0069] Example 5

[0070] Example 5 uses Figure 8 The bipolar membrane device was designed with the solutions between the electrode compartments connected in series. A 200 mL solution of 0.3 mol / L potassium sulfate was introduced into the feed compartment, a 200 mL solution of 0.6 mol / L sodium fluoride was introduced into the feed compartment, and 100 mL of heavy water was introduced into each of the acid and base compartments. During the experiment, the flow rate of the liquid in each chamber was 3 cm / s, and the current density was 50 mA / cm. 2 , the current is set to 1.1A.

[0071] The experiment was stopped when the conductivity of the liquid chamber was lower than 10mS / cm. The concentration of deuterated fluoride in the acid chamber was 0.59mol / L, and the concentration of sodium deuterium oxide was 0.50mol / L. Figure 9 shown.

[0072] As can be seen from the above examples, the present invention provides a simple method for preparing deuterated acids using a bipolar membrane device. By optimizing the feeding method, current density, volume ratio, membrane surface flow rate, etc., high-concentration deuterated acids are prepared, which provides a new route for the large-scale continuous preparation of deuterated acids. This process does not require a catalyst, the conditions are mild and controllable, the equipment is highly integrated, and the heavy water used can be reused to the greatest extent, which has important industrial application value.

[0073] The above description of the disclosed embodiments will enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A device for preparing deuterated acid using a bipolar membrane device, characterized in that: include: Bipolar membrane stack, power supply, peristaltic pump; The bipolar membrane stack is composed of bipolar membranes, cation exchange membranes, anion exchange membranes, which are alternately arranged and separated by a plastic grid, and cathode and anode electrode plates on both sides; the cathode and anode electrode plates are respectively connected to the positive and negative electrodes of a power source, wherein an anode chamber is formed between the anode electrode plate and the bipolar membrane, and a cathode chamber is formed between the cathode electrode plate and the bipolar membrane; the arrangement order from the anode to the cathode of the bipolar membrane stack is bipolar membrane-anion exchange membrane-cation exchange membrane-bipolar membrane to form a repeating unit, forming an acid chamber-salt chamber-alkali chamber in sequence; the anode chamber is connected to the cathode chamber, and is connected to a polar chamber liquid storage tank containing a strong electrolyte, and under the drive of a peristaltic pump, the solutions in the feed liquid chamber, the acid chamber, the alkali chamber, the anode chamber and the cathode chamber form a circulation flow between the bipolar membrane stack and the connected storage tanks.

2. The device for preparing deuterated acid from a bipolar membrane device according to claim 1, characterized in that: The cathode and anode electrode plates are made of titanium coated with ruthenium.

3. The device for preparing deuterated acid from a bipolar membrane device according to claim 1, characterized in that: The bipolar membrane in the bipolar membrane stack is a special ion exchange membrane with a sandwich structure consisting of a cation membrane layer, a catalyst layer, and a cathodic membrane layer. When assembled, the cation membrane layer faces the cathode, and the cathodic membrane layer faces the anode.

4. A method for preparing deuterated acid using a bipolar membrane device, characterized in that: The following steps are involved: The device for preparing deuterated acid using the bipolar membrane device according to any one of claims 1 to 3 dissociates heavy water molecules into deuterium ions and deuteroxide ions under the action of an electric field, and then combines the deuterium ions with anions passing through an anion exchange membrane to form deuterated acid in an acid chamber.

5. The method for preparing deuterated acid using a bipolar membrane device according to claim 4, characterized in that: All ion exchange membranes in the bipolar membrane device for preparing deuterated acid are first subjected to system transition; the system transition is specifically carried out as follows: Transition from water system to heavy water system.

6. The method for preparing deuterated acid using a bipolar membrane device according to claim 5, characterized in that: The process of transitioning from the water system to the heavy water system is specifically as follows: The ion exchange membrane was sequentially soaked in 20% heavy water, 40% heavy water, 60% heavy water, and 80% heavy water for 1 h to 3 h respectively, and then soaked in 100% heavy water for 20 h to 30 h.

7. The method for preparing deuterated acid using a bipolar membrane device according to claim 4, characterized in that: The apparatus for preparing deuterated acid using a bipolar membrane device is placed in a glove box during operation to prevent water molecules in the air from dissolving into the prepared deuterated acid.

8. The method for preparing deuterated acid using a bipolar membrane device according to claim 4, characterized in that: The solvent in the system is heavy water.

9. The method for preparing deuterated acid using a bipolar membrane device according to claim 4, characterized in that: The anions are provided by a strong electrolyte; the strong electrolyte is selected from one or more of K2SO4, Na2SO4, Li2SO4, KNO3, NaNO3, LiNO3, KCl, NaCl, LiCl, LiF, NaF, and KF.

10. The method for preparing deuterated acid using a bipolar membrane device according to claim 4, characterized in that: The flow rate of the liquid in each chamber is 1cm / s~10cm / s, constant current operation, and the current density is 40mA / cm 2 ~120mA / cm 2 , the current is set to 1A~1.2A.

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