A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas.

Abstract

This invention discloses a method for preparing deuterium-hydrogen water by mixing deuterium-containing water with hydrogen gas. The invention relates to a dedicated hydrogen production device and its preparation method, particularly a device and method for mixing deuterium-containing water with hydrogen gas through an ultrafiltration filter to increase the hydrogen content of the mixed water. This device utilizes the small pore size of the ultrafiltration membrane fibers to mix hydrogen gas with deuterium-containing water at a pressure of 1-4 MPa, thereby increasing the fusion of hydrogen and water. The discharged mixed water has a hydrogen content of 3000-4800 PPB. Using a manual / automatic bottling system, the resulting hydrogen-water mixture can be stored for up to 24 months, with the hydrogen content remaining above 2000 PPB.

Description

Technical Field

[0001] This invention relates to the field of hydrogen-containing deuterium water preparation technology, and in particular to a method for preparing low-deuterium hydrogen water by mixing low-deuterium water with hydrogen gas. Background Technology

[0002] Deuterium-depleted water, abbreviated as DDW, is a type of water with a low deuterium content, also known as light hydrogen water or ultralight water. A water molecule consists of two hydrogen atoms and one oxygen atom. Hydrogen atoms have three isotopes: protium (H, hydrogen), deuterium (D, heavy hydrogen), and tritium (T, superheavy hydrogen). Deuterium constitutes approximately 0.015% of the natural environment; water in which deuterium replaces hydrogen atoms is called heavy water. The low deuterium content of deuterium-depleted water is considered potentially beneficial to human health. Some studies suggest that deuterium-depleted water may possess biological effects such as anti-tumor, antioxidant, blood sugar-lowering, and antidepressant properties.

[0003] A system and method for preparing low-deuterium hydrogen-rich water (Chinese Patent Application No.: CN202010428490.0) belongs to the field of drinking water production. It includes a raw material hydrogen storage tank (1), characterized in that the raw material hydrogen storage tank (1) is connected to the air inlet (53) of the gas lift mixer, the low-deuterium water storage tank (4) is connected to the water inlet (51) of the gas lift mixer, the gas-liquid two-phase compressor (6) is connected to the water jet cavitation gas-liquid mixer (7), the low-deuterium hydrogen-rich water collection tank (13) is connected to the low-deuterium hydrogen-rich water storage tank (11), the hydrogen recovery tank (9) is connected to the low-deuterium hydrogen-rich water storage tank (11) and the hydrogen purification and pressurization unit (14), and the hydrogen purification and pressurization unit (14) is connected to the raw material hydrogen storage tank (1).

[0004] A method for preparing low-deuterium hydrogen water and its application (Chinese Patent Application No.: CN202011618767.2) includes the following steps: 1) Preparing low-deuterium hydrogen gas: using low-deuterium water as a raw material to generate low-deuterium hydrogen gas; 2) Infusing hydrogen gas into low-deuterium water: infusing the low-deuterium hydrogen gas obtained in step 1) into low-deuterium water and mixing it evenly to obtain low-deuterium hydrogen water; 3) Filling. The low-deuterium hydrogen water, its preparation method, and its application provided by this invention are the first to prepare low-deuterium hydrogen gas, and using it as a raw material, mixing it with low-deuterium water to produce low-deuterium hydrogen water. The low-deuterium hydrogen water made from low-deuterium water has a low deuterium content.

[0005] Traditional methods for preparing deuterium-rich hydrogen water suffer from problems such as low hydrogen solubility, poor mixing efficiency, and short storage time. This invention aims to improve the mixing efficiency of hydrogen and deuterium-rich water, increase the hydrogen content in the mixed water, and extend the storage time through a novel dedicated hydrogen production device. Summary of the Invention

[0006] In view of the problems pointed out in the background art and the shortcomings of the existing technology, the purpose of this invention is to provide a method for preparing deuterium-hydrogen water by mixing deuterium-hydrogen water with hydrogen gas. The deuterium-hydrogen water prepared by this method can be stored for up to 24 months, and the hydrogen content is maintained above 2000 PPB.

[0007] The above-mentioned objective is achieved through the following solution:

[0008] A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps:

[0009] Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed out through the ultrafiltration filter, which reduces the original gas and water molecules and increases the compatibility of hydrogen and water. The mixed water is then bottled through a manual or automatic bottling system.

[0010] Furthermore, the deuterium content in the low-deuterium water is no more than 120 ppm.

[0011] Furthermore, the molar ratio of the deuterium-rich water to hydrogen is 1000-1000000:1.

[0012] Furthermore, the system is pressurized to 1-4 MPa.

[0013] Furthermore, the filter membrane in the ultrafiltration filter is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-rich water through small-pore membrane fibers.

[0014] Furthermore, the hybrid matrix membrane includes the following steps:

[0015] Step 1: Mix 100-120 parts by weight of ethanol with 20-30 parts by weight of deionized water, heat the mixture to 70-77°C under stirring, then add 4-10 parts of propylene-based Pebax 2533 polyether block amide material and stir for 5-8 hours to obtain a propylene-based Pebax 2533 solution.

[0016] Step 2: By weight, mix 6-12 parts of ZIF-8 nanoparticles, 100-200 parts of deionized water, and 1-3 parts of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane (CAS: 61614-55-9) at 40-50℃ for 2-3 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds.

[0017] Step 3: Add ZIF-93 nanoparticles containing silane bonds to the propylene-containing Pebax2533 solution prepared in Step 1, add 0.003-0.03 parts of caster catalyst, and ultrasonically stir and mix at 40-50°C for 50-100 minutes. Then add 0.003-0.03 parts of aminoferrocene and 0.03-0.3 parts of sodium ethoxide, and ultrasonically stir and mix at 40-50°C for 20-30 minutes to obtain a casting solution containing filler.

[0018] Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 60-80℃ for 10-20 hours. Afterward, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

[0019] Furthermore, the preparation method of the propylene-containing Pebax 2533 is as follows:

[0020] Pebax 2533 was modified by placing it in an RF plasma generator and treating it with acrylic acid vapor at a flow rate of 10-20 ml / min for 50-100 seconds to obtain propylene-based Pebax 2533.

[0021] Furthermore, the plasma modification conditions are as follows: the plasma equipment and the radio frequency power source are at a frequency of 13.5MHz.

[0022] Furthermore, the hydrogen content of the mixed water discharged after passing through the ultrafiltration filter is 3000PPB-4800PPB.

[0023] Technical effects:

[0024] 1. Improved the mixing efficiency of hydrogen and deuterium-rich water, with the hydrogen content of the mixed water reaching 3000PPB-800PPB;

[0025] 2. A novel hybrid matrix membrane is employed. First, ZIF-8 nanoparticles containing silane-hydrogen bonds undergo a hydrosilylation reaction with Pebax 1657 containing propylene groups. This is a chemical reaction in which the Si-H unit of a hydrosilane is added to the C=C double bond of an olefin. Then, its epoxy group reacts with aminoferrocene to form an amino-epoxy group, resulting in a hybrid matrix membrane. In the preparation of this hybrid matrix membrane, a metal-organic framework (MOF), namely ZIF-8, is introduced into the polymer chain through this reaction to improve its performance.

[0026] 3. Adding ZIF-8 nanoparticles to Pebax 1657 significantly improves membrane permeability and enhances thermal and mechanical stability: The addition of nanoparticles and polymers improves the membrane's thermal and mechanical stability. This means the membrane can be used over a wider temperature range and is more resilient to physical stress, thus extending its lifespan and expanding its application range.

[0027] 4. The mixed water can be stored for up to 24 months, with the hydrogen content maintained above 2000 PPB, meeting the requirements for long-term storage. Detailed Implementation

[0028] In view of the shortcomings of the prior art, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention, which will be further explained below, including its implementation process and principles.

[0029] Example 1

[0030] A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps:

[0031] Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed out through the ultrafiltration filter, which reduces the original gas and water molecules and increases the compatibility of hydrogen and water. The mixed water is then bottled through a manual or automatic bottling system.

[0032] The deuterium content in the low-deuterium water is no more than 120 ppm.

[0033] The molar ratio of the deuterium-rich water to hydrogen is 1000:1.

[0034] The system is pressurized to 1 MPa.

[0035] The ultrafiltration filter membrane is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-rich water through small-pore membrane fibers.

[0036] The hybrid matrix membrane includes the following steps:

[0037] Step 1: Mix 100g of ethanol with 20g of deionized water and heat it to 70°C with stirring. Then add 4g of propylene-based Pebax 2533 polyether block amide material and stir for 5 hours to obtain a propylene-based Pebax 2533 solution.

[0038] Step 2: Mix 6g of ZIF-8 nanoparticles, 100g of deionized water, and 1g of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane (CAS: 61614-55-9) at 40℃ for 2 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds.

[0039] Step 3: Add ZIF-93 nanoparticles containing silane bonds to the propylene-based Pebax2533 solution prepared in Step 1, add 0.003g of caster catalyst, and ultrasonically stir and mix at 40°C for 50 minutes. Then add 0.003g of aminoferrocene and 0.03g of sodium ethoxide, and ultrasonically stir and mix at 40°C for 20 minutes to obtain a casting solution containing filler.

[0040] Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 60°C for 10 hours. Subsequently, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

[0041] The preparation method of the propylene-containing Pebax 2533 is as follows:

[0042] Pebax 2533 was modified in an RF plasma generator and treated with acrylic acid vapor at a flow rate of 10 ml / min for 50 seconds to obtain propylene-containing Pebax 2533.

[0043] The plasma modification conditions are as follows: the plasma equipment and the radio frequency power source are at a frequency of 13.5MHz.

[0044] Example 2

[0045] A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps:

[0046] Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed out through the ultrafiltration filter, which reduces the original gas and water molecules and increases the compatibility of hydrogen and water. The mixed water is then bottled through a manual or automatic bottling system.

[0047] The deuterium content in the low-deuterium water is no more than 120 ppm.

[0048] The molar ratio of the deuterium-rich water to hydrogen is 10000:1.

[0049] The system is pressurized to 2 MPa.

[0050] The ultrafiltration filter membrane is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-rich water through small-pore membrane fibers.

[0051] The hybrid matrix membrane includes the following steps:

[0052] Step 1: Mix 110g of ethanol with 25g of deionized water and heat it to 72°C under stirring. Then add 6g of propylene-based Pebax 2533 polyether block amide material and stir for 6 hours to obtain a propylene-based Pebax 2533 solution.

[0053] Step 2: Mix 8g of ZIF-8 nanoparticles, 135g of deionized water, and 2g of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane (CAS: 61614-55-9) at 45℃ for 2 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds.

[0054] Step 3: Add ZIF-93 nanoparticles containing silane bonds to the propylene-based Pebax2533 solution prepared in Step 1, add 0.01g of caster catalyst, and mix by ultrasonic stirring at 45°C for 75 minutes. Then add 0.01g of aminoferrocene and 0.1g of sodium ethoxide, and mix by ultrasonic stirring at 45°C for 25 minutes to obtain a casting solution containing filler.

[0055] Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 70°C for 15 hours. Subsequently, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

[0056] The preparation method of the propylene-containing Pebax 2533 is as follows:

[0057] Pebax 2533 was modified by placing it in an RF plasma generator and treating it with acrylic acid vapor at a flow rate of 15 ml / min for 75 seconds to obtain propylene-based Pebax 2533.

[0058] The plasma modification conditions are as follows: the plasma equipment and the radio frequency power source are at a frequency of 13.5MHz.

[0059] Example 3

[0060] A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps:

[0061] Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed out through the ultrafiltration filter, which reduces the original gas and water molecules and increases the compatibility of hydrogen and water. The mixed water is then bottled through a manual or automatic bottling system.

[0062] The deuterium content in the low-deuterium water is no more than 120 ppm.

[0063] The molar ratio of the deuterium-rich water to hydrogen is 100,000:1.

[0064] The system is pressurized to 3 MPa.

[0065] The ultrafiltration filter membrane is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-rich water through small-pore membrane fibers.

[0066] The hybrid matrix membrane includes the following steps:

[0067] Step 1: Mix 110g of ethanol with 25g of deionized water and heat it to 74°C under stirring. Then add 8g of propylene-based Pebax 2533 polyether block amide material and stir for 7 hours to obtain a propylene-based Pebax 2533 solution.

[0068] Step 2: Mix 10g of ZIF-8 nanoparticles, 170g of deionized water, and 2g of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane (CAS: 61614-55-9) at 45℃ for 3 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds.

[0069] Step 3: Add ZIF-93 nanoparticles containing silane bonds to the propylene-based Pebax2533 solution prepared in Step 1, add 0.02g of caster catalyst, and mix by ultrasonic stirring at 45°C for 75 minutes. Then add 0.02g of aminoferrocene and 0.2g of sodium ethoxide, and mix by ultrasonic stirring at 45°C for 25 minutes to obtain a casting solution containing filler.

[0070] Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 70°C for 15 hours. Subsequently, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

[0071] The preparation method of the propylene-containing Pebax 2533 is as follows:

[0072] Pebax 2533 was modified by placing it in an RF plasma generator and treating it with acrylic acid vapor at a flow rate of 15 ml / min for 75 seconds to obtain propylene-based Pebax 2533.

[0073] The plasma modification conditions are as follows: the plasma equipment and the radio frequency power source are at a frequency of 13.5MHz.

[0074] Example 4

[0075] A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps:

[0076] Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed out through the ultrafiltration filter, which reduces the original gas and water molecules and increases the compatibility of hydrogen and water. The mixed water is then bottled through a manual or automatic bottling system.

[0077] The deuterium content in the low-deuterium water is no more than 120 ppm.

[0078] The molar ratio of the deuterium-rich water to hydrogen is 1,000,000:1.

[0079] The system is pressurized to 4 MPa.

[0080] The ultrafiltration filter membrane is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-rich water through small-pore membrane fibers.

[0081] The hybrid matrix membrane includes the following steps:

[0082] Step 1: Mix 120g of ethanol with 30g of deionized water and heat it to 77°C with stirring. Then add 10g of propylene-based Pebax 2533 polyether block amide material and stir for 8 hours to obtain a propylene-based Pebax 2533 solution.

[0083] Step 2: Mix 12g of ZIF-8 nanoparticles, 200g of deionized water, and 3g of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane (CAS: 61614-55-9) at 50°C for 3 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds.

[0084] Step 3: Add ZIF-93 nanoparticles containing silane bonds to the propylene-containing Pebax2533 solution prepared in Step 1, add 0.03g of caster catalyst, and ultrasonically stir and mix at 50°C for 100 minutes. Then add 0.03g of aminoferrocene and 0.3g of sodium ethoxide, and ultrasonically stir and mix at 50°C for 30 minutes to obtain a casting solution containing filler.

[0085] Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 80°C for 20 hours. Subsequently, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

[0086] The preparation method of the propylene-containing Pebax 2533 is as follows:

[0087] Pebax 2533 was modified in an RF plasma generator and treated with acrylic acid vapor at a flow rate of 20 ml / min for 100 seconds to obtain propylene-containing Pebax 2533.

[0088] The plasma modification conditions are as follows: the plasma equipment and the radio frequency power source are at a frequency of 13.5MHz.

[0089] Comparative Example 1

[0090] This example is a comparative example of Example 1, and is basically the same as Example 1, except that an equal amount of Pebax 2533 was used to replace the propylene-based Pebax 2533 in the process of preparing the mixed matrix membrane.

[0091] Comparative Example 2

[0092] This example is a comparative example of Example 1, and is basically the same as Example 1, except that 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane is not added during the preparation of the mixed matrix membrane.

[0093] The hydrogen content of the mixed water prepared in the above embodiments was determined by gas chromatography, and the test results are as follows:

[0094]

[0095]

[0096] As can be seen from the data of the above specific implementation scheme, this method achieves increased fusion of hydrogen and water, and the hydrogen content of the discharged mixed water reaches 3000PPB-4800PPB. After storage for 24 months, the hydrogen content remains above 2000PPB.

[0097] The above examples illustrate the present invention only to aid in understanding it and are not intended to limit the scope of the invention. Those skilled in the art can make various simple deductions, modifications, or substitutions based on the principles of this invention.

Claims

1. A method for preparing deuterium-hydrogen water by mixing deuterium-rich water with hydrogen gas, comprising the following steps: Low-deuterium water and hydrogen are introduced into an ultrafiltration filter in a certain proportion. The system is pressurized so that the hydrogen and low-deuterium water are mixed and squeezed through the ultrafiltration filter to improve the compatibility of hydrogen and low-deuterium water. The mixed water is then bottled through a manual or automatic bottling system. The ultrafiltration filter membrane is a mixed matrix membrane, which achieves thorough mixing of hydrogen and deuterium-free water through small-pore membrane fibers; the mixed matrix membrane includes the following steps: Step 1: Mix 100-120 parts by weight of ethanol with 20-30 parts by weight of deionized water, heat the mixture to 70-77°C under stirring, then add 4-10 parts of propylene-based Pebax 2533 polyether block amide material and stir for 5-8 hours to obtain a propylene-based Pebax 2533 solution. Step 2: By weight, mix 6-12 parts of ZIF-8 nanoparticles, 100-200 parts of deionized water, and 1-3 parts of 2,4,6,8-tetramethyl-2-[3-(epoxyethylene methoxy)propyl]cyclotetrasiloxane, stir at 40-50℃ for 2-3 hours, filter, and dry to obtain ZIF-8 nanoparticles containing silicon-hydrogen bonds. Step 3: Add ZIF-8 nanoparticles containing silane bonds to the propylene-based Pebax 2533 solution prepared in Step 1, add 0.003-0.03 parts of caster catalyst, and ultrasonically stir and mix at 40-50°C for 50-100 minutes. Then add 0.003-0.03 parts of aminoferrocene and 0.03-0.3 parts of sodium ethoxide, and ultrasonically stir and mix at 40-50°C for 20-30 minutes to obtain a casting solution containing filler. Step 4: The casting solution obtained in Step 3 is ultrasonically treated, then poured into a clean polytetrafluoroethylene plate and dried at 60-80℃ for 10-20 hours. Afterward, the oven is evacuated to remove the solvent and a mixed matrix membrane is obtained.

2. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The deuterium content in the low-deuterium water is no more than 120 ppm.

3. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The molar ratio of the deuterium-rich water to hydrogen is 1000-1000000:

1.

4. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The system is pressurized to 1-4 MPa.

5. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The preparation method of the propylene-based Pebax 2533 polyether block amide material is as follows: Pebax 2533 was modified in an RF plasma generator and treated with acrylic acid vapor at a flow rate of 10-20 mL / min for 50-100 seconds to obtain propylene-based Pebax 2533 polyether block amide material.

6. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The plasma modification conditions are: the plasma equipment and the radio frequency power source are 13.5MHz.

7. The method for preparing deuterium-hydrogen water by mixing deuterium-rich water and hydrogen gas according to claim 1, characterized in that: The hydrogen content of the mixed water discharged after passing through the ultrafiltration filter is 3000PPB-4800PPB.

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