Method for preparing deuterium-depleted water through cooperation of magnetic resonance and electrolysis strengthening

Abstract

The invention discloses a method for preparing deuterium-depleted water through cooperation of magnetic resonance and electrolysis strengthening, and particularly relates to the technical field of deuterium-depleted water preparation, and the method comprises the following steps: S1, injecting water to be treated into a magnetic resonance reaction chamber, and carrying out magnetic resonance treatment, so that the vibration energy level of a deuterium-oxygen bond is improved through a nuclear magnetic resonance effect, the bond energy is enhanced to 5.0-5.2 eV, and the deuterium-depleted water is obtained; forming a metastable-state deuterium-containing water molecular structure; s2, the water subjected to magnetic resonance treatment is guided into a three-electrode electrolytic bath for pre-electrolysis, then a gradient voltage electrolysis process is adopted for reinforced electrolysis to form a deuterium concentration gradient, and therefore hydrogen and electrolytic residual liquid are separated; and S3, finally performing gas-liquid isotope fractionation to finally prepare the deuterium-depleted water. According to the method, deuterium-oxygen bond energy is enhanced through magnetic resonance pretreatment, low-temperature gradient electrolysis and vacuum rectification are combined, a magnetoelectric synergistic isotope separation system is constructed, and the method has the advantages that the separation efficiency can be improved, the energy consumption can be reduced, the separation coefficient can be improved, the material utilization rate can be improved, and the deuterium content of the prepared deuterium-depleted water is lower than 30 ppm.

Description

Technical Field

[0001] The present invention relates to the technical field of deuterium-depleted water preparation, and more particularly to a method for preparing deuterium-depleted water by using magnetic resonance synergistic electrolysis enhancement. Background Art

[0002] Due to its unique biological activity and medical value, deuterium-depleted water is increasingly in demand in areas such as tumor adjuvant therapy and cell culture.

[0003] Among existing preparation technologies, electrolysis can achieve deuterium enrichment by utilizing the isotope kinetic effect (the electrolysis rate of deuterium is about 10% slower than that of hydrogen), but the traditional electrolysis process has the following drawbacks:

[0004] The separation coefficient is low (only 1.1-1.3), and multi-stage electrolysis is required to achieve effective separation;

[0005] High energy consumption (DC power consumption of 5-8kWh / m 3 );

[0006] Electrode polarization leads to side reactions (such as oxygen evolution reaction), which affects the purity of the product.

[0007] In order to break through the above bottleneck, we combine magnetic resonance bond energy control technology with low-temperature electrolysis, enhance the isotope separation effect through the synergistic effect of magnetic field and electric field, and construct a three-level enhancement system of "molecular bond energy control-directional charge transfer-gas-liquid isotope fractionation" to achieve efficient preparation of deuterium-depleted water. Therefore, a method for preparing deuterium-depleted water by magnetic resonance synergistic electrolysis is proposed. Summary of the Invention

[0008] In order to overcome the above-mentioned defects of the prior art, the present invention provides a method for preparing deuterium-depleted water by using magnetic resonance synergistic electrolysis to solve the problems raised in the above-mentioned background technology.

[0009] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement, comprising the following steps:

[0010] S1: Injecting the water to be treated into the magnetic resonance reaction chamber for magnetic resonance treatment, thereby increasing the vibration energy level of the deuterium-oxygen bond through the nuclear magnetic resonance effect, and enhancing the bond energy to 5.0-5.2 eV, forming a metastable deuterium-containing water molecular structure;

[0011] S2: introducing the magnetic resonance treated water into a three-electrode electrolytic cell and electrolyzing it using a gradient voltage electrolysis process to form a deuterium concentration gradient;

[0012] S3: Finally, gas-liquid isotope fractionation is performed to finally prepare deuterium-depleted water.

[0013] The magnetic field intensity of the magnetic resonance treatment in S1 is 0.3-0.5T, a pulsed radio frequency of 1.2-1.5GHz and a power of 600-1000W is applied, the treatment time is 8-15 minutes, and the pulse duty cycle of the magnetic resonance treatment is 30%-50%.

[0014] The deuterium oxygen (DO) bond energy was enhanced by magnetic resonance pretreatment to 5.0-5.2 eV (8%-12% higher than that of natural water), forming a metastable deuterated water molecular structure. In this process, the deuterium nuclear spin-lattice relaxation time was adjusted, and the vibration mode of the DO bond was changed from in-plane bending vibration (1210 cm -1 ) symmetrical stretching vibration (2670cm -1 ) coupling, bond length shortening Density functional theory (DFT) calculations verified an 18% increase in bond energy. Utilizing the enhanced D-O bond energy barrier after magnetic resonance treatment, pre-electrolysis (low voltage, high temperature) in a three-electrode electrolyzer preferentially breaks hydrogen-oxygen (HO) bonds. Deuterium-containing water molecules are then enriched at the cathode through enhanced electrolysis (high voltage, low temperature), forming a deuterium concentration gradient. Finally, deuterium is separated through multi-stage distillation in a vacuum distillation tower, utilizing the difference in saturated vapor pressure between deuterated water and light water, ultimately yielding deuterium-depleted water.

[0015] This increases the discharge overpotential of deuterium by 200 mV during the electrolysis process, improves the hydrogen evolution rate by 35%, and reduces the deuterium content by more than 60% in a single treatment. Combined with low-temperature electrolysis and vacuum distillation, the total energy consumption is lower than that of traditional processes, and the deuterium content of the final prepared low-deuterium water is ≤30 ppm, meeting the high-purity requirements of medical and industrial applications.

[0016] Preferably, the three electrodes of the three-electrode electrolytic cell include an anode coated with a titanium-based iridium oxide coating, a cathode made of a platinum-carbon alloy, and a reference electrode.

[0017] Titanium-based iridium oxide anode: strong corrosion resistance, suitable for stable oxygen evolution during electrolysis and reducing side reactions.

[0018] Platinum carbon alloy cathode (Pt / C ≥ 80 wt%): High catalytic activity, promoting hydrogen ion reduction, while suppressing deuterium (D + ) discharge.

[0019] Reference electrode: Precisely control the electrolysis voltage to ensure the stability of the gradient voltage process.

[0020] This enables the deuterium content of the generated hydrogen to be less than 5ppm, and the purity of the hydrogen to be increased to above 99.99% (98.5% in traditional processes), reducing interference from impurities. The titanium-based iridium oxide and platinum-carbon alloy materials have strong corrosion resistance, reducing the frequency of consumable replacement and saving costs.

[0021] Preferably, the gradient voltage electrolysis process in S2 includes:

[0022] Pre-electrolysis stage: Apply a constant voltage of 1.8-2.0V and control the electrolyte temperature at 10-15°C to preferentially break the hydrogen-oxygen bond and generate hydrogen with a deuterium content of less than 5ppm;

[0023] Enhanced electrolysis stage: The voltage is raised to 2.2-2.5V, and the temperature is reduced to 5-8°C. The enhanced bond energy barrier of the deuterium-oxygen bond is utilized to enrich the deuterium-containing water molecules on the cathode surface, forming a deuterium concentration gradient. The deuterium content in the liquid phase can be increased to 1.5-2 times the initial level.

[0024] Through the coordinated regulation of temperature and voltage, the directional separation of deuterium and hydrogen is achieved, avoiding the inefficiency of traditional constant-voltage electrolysis; the low-temperature environment inhibits side reactions (such as oxygen evolution reaction), reduces energy loss, and the DC power consumption is ≤4kWh / m 3 .

[0025] Preferably, the electrolysis time of the pre-electrolysis stage is 0-10 min, and the electrolysis time of the enhanced electrolysis stage is 10-30 min.

[0026] By controlling the time of the pre-electrolysis stage, the duration of preferential precipitation of light hydrogen can be controlled to avoid deuterium loss due to excessive electrolysis; and by strengthening the time control of the electrolysis stage, it can ensure that deuterium-containing water molecules are fully enriched, forming a sufficient deuterium concentration gradient, providing a basis for subsequent distillation.

[0027] Therefore, the pre-electrolysis time can be adjusted according to the initial deuterium content of the raw water. For example, natural water requires 10 minutes, while high-concentration heavy water can be shortened to 0 minutes. Sufficient enhanced electrolysis time ensures that the deuterium concentration gradient on the cathode surface is maximized, thereby improving the separation effect of subsequent distillation.

[0028] Preferably, the gas-liquid isotope fractionation in S3 comprises the following steps:

[0029] The oxygen released from the anode is directly discharged after condensation and water removal, thus removing trace deuterium-containing gas;

[0030] The hydrogen generated at the cathode is purified by a palladium membrane and then recycled, achieving a closed-loop material cycle and reducing waste.

[0031] The residual electrolyte enters the vacuum distillation tower, and the difference in saturated vapor pressure between deuterated water and light water is used to gradually reduce the deuterium content through 3-5 levels of distillation, ultimately producing low-deuterium water with a deuterium content of less than or equal to 30 ppm.

[0032] The pressure of the vacuum distillation tower is controlled at 0.01-0.05 MPa, and the temperature is controlled at 50-70°C.

[0033] The saturated vapor pressure difference ΔP between the deuterated water and light water is 0.8-1.2 kPa.

[0034] The temperature difference between adjacent stages of the 3-5 stage gradient temperature distillation is 5-10° C., which is used to achieve multi-stage fractionation of isotopes.

[0035] By utilizing the difference in saturated vapor pressure between deuterated water and light water, through 3-5 levels of gradient temperature distillation, light water evaporates first, and deuterium in the residual liquid is gradually enriched and separated, ensuring that light water and deuterated water are effectively separated during the distillation process. After multi-stage distillation, the deuterium content can be significantly reduced. Through the low-pressure environment, that is, the air pressure is controlled at 0.01-0.05MPa, the boiling point of water can be lowered, energy consumption can be reduced, and the damage to equipment caused by high temperature can be avoided. The temperature is controlled at 50-70℃, so that the vapor pressure difference between light water and deuterated water is maximized at a low boiling point, thereby improving the distillation efficiency.

[0036] Technical effects and advantages of the present invention:

[0037] 1. Magnetic resonance pretreatment is used to improve the electrolysis separation coefficient. By regulating the bond energy, the difference in the deuterium hydrogen electrolysis rate is increased from the traditional 10% to 25%-30%, and the separation coefficient α exceeds 2.0 (traditional electrolysis α = 1.15). In addition, by increasing the deuterium oxygen bond energy through magnetic resonance, the deuterium retention rate during the electrolysis process is increased from 85% to 92%. A single treatment can reduce the deuterium content by more than 60%;

[0038] 2. By adopting the hierarchical voltage-temperature control strategy, the energy consumption is reduced (DC power consumption ≤ 4kWh / m 3 ) while suppressing side reactions, the purity of hydrogen is increased to more than 99.99%. The total energy consumption of low-temperature electrolysis combined with vacuum distillation is reduced by 55% compared with the traditional distillation-electrolysis combined process, and the production cost is reduced to US$1.2 / L, which is significantly reduced compared to the traditional process of US$2.8 / L.

[0039] 3. The hydrogen generated by electrolysis can be purified and used as fuel cell raw material. The deuterium gas in the distillation tail gas is recovered through catalytic exchange, and the material utilization rate is greater than 98%.

[0040] 4. It can process a wide concentration range from natural water (150ppm) to industrial heavy water (>5000ppm), and output a series of products with adjustable deuterium content of 5-50ppm. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 Flow chart of the method of the present invention. DETAILED DESCRIPTION

[0042] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0043] As attached Figure 1The method for preparing deuterium-depleted water by using magnetic resonance and electrolysis enhancement shown in the figure comprises the following steps:

[0044] 1. Magnetic resonance bond energy regulation pretreatment

[0045] The treated water (initial deuterium content 150ppm ± 10%) is injected into a magnetic resonance reaction chamber with a magnetic field strength of 0.3-0.5T. A pulsed radio frequency of 1.2-1.5GHz and a power of 600-1000W (duty cycle 30%-50%) is applied for 8-15 minutes. Through the nuclear magnetic resonance effect, the vibrational energy level of the deuterium-oxygen bond (DO) is increased by 15%-20%, enhancing the bond energy to 5.0-5.2eV (an 8%-12% increase compared to natural water), forming a metastable deuterated water molecular structure.

[0046] 2. Low temperature gradient electrolysis separation

[0047] The pretreated water is introduced into a three-electrode electrolytic cell (titanium-based iridium oxide anode + platinum carbon cathode + reference electrode) and a gradient voltage electrolysis process is used:

[0048] Pre-electrolysis stage (0-10 min): Apply a constant voltage of 1.8-2.0 V and control the electrolyte temperature at 10-15°C to preferentially break the hydrogen-oxygen bond (HO) and generate hydrogen with a deuterium content of less than 5 ppm.

[0049] Enhanced electrolysis stage (10-30min): The voltage is raised to 2.2-2.5V and the temperature is lowered to 5-8°C. The enhanced bond energy barrier of the deuterium-oxygen bond is used to enrich deuterium-containing water molecules (HDO, D2O) on the cathode surface, forming a deuterium concentration gradient (the deuterium content in the liquid phase is increased to 1.5-2 times the initial level).

[0050] 3. Gas-liquid isotope fractionation

[0051] The oxygen (containing trace DO) released from the anode is directly discharged after condensation and water removal;

[0052] The hydrogen generated at the cathode is purified by a palladium membrane (99.99% purity) and then recycled;

[0053] The residual electrolyte (deuterium content 300-500ppm) enters a vacuum distillation tower (0.01-0.05MPa, 50-70℃). The deuterium content is gradually reduced through 3-5 stages of distillation by utilizing the difference in saturated vapor pressure between deuterated water and light water (ΔP = 0.8-1.2kPa). The deuterium content of the final condensed water is ≤30ppm.

[0054] Example 1

[0055] The first embodiment provides a method for preparing deuterium-depleted water by using magnetic resonance assisted electrolysis, comprising the following steps:

[0056] 1. Magnetic resonance treatment: 200L of natural water was injected into a 0.4T magnetic field reaction chamber and treated with 1.35GHz radio frequency (power 800W, duty cycle 40%) for 12 minutes. The vibration frequency of the deuterium-oxygen bond was detected to shift to a high frequency by 12cm. -1 (Bond energy increased by 15%).

[0057] 2. Gradient electrolysis:

[0058] Electrode parameters: anode area 0.5m 2 , cathode platinum carbon loading 2mg / cm 2 , the electrolyte is 0.1MNaOH:

[0059] Pre-electrolysis: 1.9V / 12℃, 10 minutes, deuterium content in collected hydrogen <3ppm;

[0060] Enhanced electrolysis: 2.4V / 6℃, 25 minutes, the deuterium content of the residual electrolytic solution increased to 450ppm.

[0061] 3. Vacuum distillation: three-stage distillation (pressure 0.03MPa, temperature 60 / 55 / 50℃ gradient), the final product has a deuterium content of 28ppm and a conductivity of <1μS / cm, in line with USP <645> Water for injection standards.

[0062] Example 2

[0063] The second embodiment provides a method for preparing deuterium-depleted water by using magnetic resonance assisted electrolysis, comprising the following steps:

[0064] By treating industrial heavy water with a deuterium content of 5000ppm, ultrapure low-deuterium water with a deuterium content of 10ppm was obtained after magnetic resonance (1.4GHz / 1000W / 15min) + gradient electrolysis (2.5V / 5℃) + five-stage distillation, with a yield of 75%, a 20% increase over the traditional method.

[0065] Comparative Example (Traditional Electrolysis)

[0066] The same raw water was electrolyzed at a constant voltage of 2.5V (temperature 25°C). After three-stage electrolysis, the deuterium content of the residual liquid was 180ppm, and the power consumption was 7.2kWh / m 3 , hydrogen purity 98.5%.

[0067] Compared with the present invention, the deuterium removal rate in the present invention is increased by 62%, energy consumption is reduced by 44%, and product purity is increased by 1.5 times.

[0068] The deuterium content and half width of the deuterium water prepared in the above examples 1 and 2 and the comparative example were tested, and the deuterium content was tested simultaneously with the low-deuterium water of the existing product. The test data are shown in Table 1 below.

[0069] Among them, the sample analysis method and the instruments and equipment used are:

[0070] Spectroscopy-Chromatography-Mass Spectrometry and Other Spectral Analysis of Unknown Objects

[0071] Some of the instruments and models used for sample analysis are:

[0072] NMR nuclear magnetic resonance spectrometer: Bruker AVANCEⅢ400, 400.13 MHz

[0073] Table 1: Deuterium content and half-amplitude detection table

[0074]

[0075] As can be seen from the above table, the deuterium content of the low-deuterium water prepared in Examples 1 and 2 is less than 30 ppm. Although the deuterium content of drinking water samples No. 1 and No. 2 is 29 ppm and 28 ppm respectively, the deuterium content is also low, but the half-value is high, which indicates that the impurity ion content is too high. The technical solution of the present application can achieve a low deuterium content while making the purity higher.

[0076] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement, characterized in that: The following steps are involved: S1: Injecting the water to be treated into the magnetic resonance reaction chamber for magnetic resonance treatment, thereby increasing the vibration energy level of the deuterium-oxygen bond through the nuclear magnetic resonance effect, and enhancing the bond energy to 5.0-5.2 eV, forming a metastable deuterium-containing water molecular structure; S2: The water after magnetic resonance treatment is introduced into a three-electrode electrolytic cell for pre-electrolysis, and then a gradient voltage electrolysis process is used to enhance electrolysis to form a deuterium concentration gradient, thereby separating hydrogen from the residual electrolytic solution; S3: Finally, gas-liquid isotope fractionation is performed to finally prepare deuterium-depleted water.

2. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 1, characterized in that: The magnetic field intensity of the magnetic resonance treatment in S1 is 0.3-0.5T, a pulsed radio frequency of 1.2-1.5GHz and a power of 600-1000W is applied, the treatment time is 8-15 minutes, and the pulse duty cycle of the magnetic resonance treatment is 30%-50%.

3. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 1, characterized in that: The three electrodes of the three-electrode electrolytic cell include an anode with a titanium-based iridium oxide coating, a cathode made of a platinum-carbon alloy, and a reference electrode.

4. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 1, characterized in that: The gradient voltage electrolysis process in S2 includes: Pre-electrolysis stage: Apply a constant voltage of 1.8-2.0V and control the electrolyte temperature at 10-15°C to preferentially break the hydrogen-oxygen bond and generate hydrogen with a deuterium content of less than 5ppm; Intensified electrolysis stage: the voltage is raised to 2.2-2.5V, the temperature is lowered to 5-8°C, and the enhanced bond energy barrier of the deuterium-oxygen bond is utilized to enrich the deuterium-containing water molecules on the cathode surface, forming a deuterium concentration gradient.

5. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 4, characterized in that: The electrolysis time of the pre-electrolysis stage is 0-10 minutes, and the electrolysis time of the enhanced electrolysis stage is 10-30 minutes.

6. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 1, characterized in that: The gas-liquid isotope fractionation in S3 comprises the following steps: The oxygen released from the anode is discharged directly after condensation and water removal; The hydrogen generated at the cathode is purified by a palladium membrane and then recycled; The residual electrolyte enters the vacuum distillation tower, and the difference in saturated vapor pressure between deuterated water and light water is used to gradually reduce the deuterium content through 3-5 levels of distillation, ultimately producing low-deuterium water with a deuterium content of less than or equal to 30 ppm.

7. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 6, characterized in that: The pressure of the vacuum distillation tower is controlled at 0.01-0.05 MPa, and the temperature is controlled at 50-70°C.

8. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 6, characterized in that: The saturated vapor pressure difference ΔP between the deuterated water and light water is 0.8-1.2 kPa.

9. The method for preparing deuterium-depleted water by magnetic resonance assisted electrolysis enhancement according to claim 6, characterized in that: The temperature difference between adjacent stages of the 3-5 stage gradient temperature distillation is 5-10° C., which is used to achieve multi-stage fractionation of isotopes.

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