TWI603777B - Device for preparing supersaturated hydrogen solution and preparation method thereof - Google Patents

Description

Preparation device of supersaturated hydrogen solution and preparation method thereof

The present invention relates to a technique and apparatus for charging a liquid with hydrogen to a supersaturated state, and more particularly to a device for preparing a supersaturated nanobubble hydrogen solution.

The hydrogen solution refers to a gas-liquid mixture formed after hydrogen is dissolved in water, and the addition of hydrogen does not change the pH of the raw water. Since 2007, Nature published a report on the biomedical effects of hydrogen, anti-inflammatory, anti-apoptotic effects of hydrogen in Japan. In the past seven years, the biological effects of hydrogen aqueous solution have gradually been accepted and recognized. Because of its high biosafety, hydrogen solution has revolutionized and actively reversed the effects of pathological damage and extremely convenient use methods (such as drinking/soaking), which has become the most interesting project in the healthcare market worldwide. one. Among them, the supersaturated hydrogen solution is particularly remarkable because of its high preparation difficulty and wide application range.

Hydrogen intake by drinking hydrogen water is currently the most widely used method and the safest and most common form of hydrogen health products. However, the solubility of hydrogen in water is very low, and it is a gas that is insoluble or even insoluble in water. Under normal temperature and normal pressure (normal temperature is 20 ° C, atmospheric pressure is 101.3 Kpa), hydrogen saturation of 1 L water is 18.2 ml or 1.6. Mg, which is usually expressed by a mass concentration of 1.6 ppm, is a barrier to drinking high-hydrogen-containing aqueous solutions in view of the fact that hydrogen is hardly soluble in water.

The preparation method of drinking hydrogen water includes electrolyzed water, hydrogen dissolved water, metal magnesium reaction water and the like.

Electrolyzed water is the earliest hydrogen water used in human body, and drinking electrolyzed water for health care originated in Japan. The equipment for preparing electrolyzed water is called an electrolysis tank. The alkaline water separated by the semi-permeable membrane after electrolysis will contain a small amount of hydrogen. The deficiency of electrolyzed water is that the drinking water is doped directly in the drinking water. The residual chlorine and ozone generated by electrolysis will change the pH value of the water, and the metal electrode of the electrolyzer directly acts on the water, and a small amount of metal ions will be precipitated. If used for drinking, the metal ions will enter the human body with water. More importantly, the hydrogen solution obtained by electrolysis of water has a low efficiency and a low solubility, which is far from the saturation state of hydrogen in an aqueous solution.

Hydrogen water can also be prepared by chemical reaction of metal and water to produce hydrogen and hydroxide at normal temperature. Many metals such as iron, aluminum, magnesium, etc. can react with water to produce hydrogen, but most metals have the disadvantages of poor mouthfeel, slow reaction rate, and significant toxicity.

Accordingly, it is an object of the present invention to provide a preparation apparatus and a preparation method for producing a supersaturated hydrogen solution at low cost and at a low speed.

The preparation principle of the invention is "micro-pipe gas-liquid two-phase flow" method, and the mechanism of supersaturation is nano bubble technology. Specifically, the gas-liquid two-phase flow method of the micro-pipe simultaneously controls the flow of the gas and the liquid, and the gas is dispersed into small bubbles of uniform size by the shear force between the liquid and the gas, and the micro-pipeline gas-liquid two-phase flow method generates micro-flow. The bubble is mainly caused by the shear force between the liquid and the gas, and the size of the microbubble generated can be equal to or even smaller than that of the microchannel (the small hole of the hollow membrane wall).

The invention breaks through the saturated solubility of hydrogen under normal temperature and normal pressure, and prepares Supersaturated nanobubble hydrogen solution. The saturated concentration of hydrogen dissolved water at normal temperature and pressure is 1.6 ppm, and the concentration of supersaturated hydrogen water obtained by the method of the invention can be increased by 2 to 4 times; the combination of gas-liquid mixer (multi-stage series or parallel) is also A substantial increase in the amount of supersaturated nanobubble hydrogen solution per unit time lays the foundation.

The hydrogen generator of the invention is completely isolated from the drinking water, and is electrolyzed by a proton exchange membrane pure water electrolysis method, and the hydrogen and the solution which are electrolyzed according to the GB31633-2014 standard are fused by the above-mentioned nanobubble to produce a supersaturated hydrogen solution.

The present invention adopts a "micro-pipe gas-liquid two-phase flow method" to select a membrane element, particularly a hollow fiber membrane, as a nano-bubble generating device. In order to prepare supersaturated hydrogen solution conveniently and efficiently, research and optimization have been made on membrane elements, especially hollow fiber membrane material selection, membrane structure, membrane group structure, etc., among which: The selection of hollow fiber membrane materials: According to research, Preferably, the organic polymer polymer synthetic membrane has the characteristics of uniform pore size distribution, high membrane resistance, high gas passage rate, and certain strong hydrophobicity, and the optional hydrophobic materials are polypropylene (PP) and polyvinylidene fluoride. Ethylene (PVDF), polyethylene (PE), polyfluorene (PS), polydecylamine (PA), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyether oxime (PES), etc.; The film can be made hydrophilic by doping a polymer with a hydrophilic hydrophilic material such as polymethyl methacrylate (PHEMA), polyacrylamide (PAM) or polyvinylpyrrolidone (PVP) with a large amount of hydrophilic groups. Sexual and hydrophobic characteristics; Membrane structure selection: According to research, it is preferred that the shape is close to the standard circle, the density of the inner and outer walls is asymmetric, the inner diameter is between 40μm and 400μm, the wall thickness is 20~50μm, and the porosity is 30%~70. %, hollow fiber membrane with a membrane pore size of 1 nm to 1 μm. Membrane group structure selection: The number and length of hollow fibers in the membrane group determine the membrane surface area. Considering the volume factor, the membrane surface area is preferably 0.5m ² ~ 2m ² (the number of hollow fibers is 8000~15000); if super-saturated hydrogen is to be added The preparation time of the solution per unit time, multiple membrane groups can be connected in series or in parallel; considering the actual use environment of the equipment, the membrane group length is 5cm~100cm, the diameter is 10mm~500mm; the main parameters of the preparation process: ambient temperature: prepared according to the invention The supersaturated nano-bubble hydrogen solution can be implemented at normal temperature without special ambient temperature; the gas path pressure: while the hydrogen generator generates hydrogen, in order to ensure the concentration of the super-saturated nano-hydrogen solution, the gas-liquid mixer is preferably introduced. The end maintains a pressure of 0.05MPa~0.6MPa; the liquid pressure: the liquid pressure is close to the normal pressure; the liquid flow rate: to ensure the concentration of the supersaturated nano hydrogen solution and the immediate preparation efficiency, the liquid flow rate of the liquid discharge port is preferably 0.200~2L/ Minute range.

The selection of the structure, material, and the like of the above membrane element is mainly explained based on the hollow fiber membrane group. However, it should be understood that the membrane element of the apparatus for preparing a supersaturated hydrogen solution of the present invention may also select one or more of plate-and-plate, roll, fold and tubular membrane elements.

According to an aspect of the present invention, there is provided a device for preparing a supersaturated hydrogen solution, the preparation device comprising a casing and a hollow fiber membrane group, wherein the casing is provided with a liquid inlet connected to a liquid source, An air inlet and a liquid discharge port communicating with a hydrogen gas source, the hollow fiber membrane group includes a plurality of hollow fiber membrane tubes and housed in the casing, and an inlet end of the hollow fiber membrane group is connected to the liquid inlet Thereby liquid can flow inside the hollow fiber membrane tube, and hydrogen gas from the hydrogen source can flow from the membrane pore of the hollow fiber membrane tube into the interior of the hollow fiber membrane tube and mix with the liquid, and An outlet end of the hollow fiber membrane group is in communication with the liquid discharge port.

In one embodiment, the liquid may be a low viscosity liquid such as water, carbonated beverage, tea beverage, functional beverage, coffee beverage or alcoholic beverage.

In one embodiment, the hollow fiber membrane tube may have a wall thickness of 20-50 μm.

In one embodiment, the hollow fiber membrane tube may have a porosity of from 30% to 70%, preferably from 40% to 50%.

In one embodiment, the hollow fiber membrane may have an inner diameter of 40 μm to 400 μm, preferably 150 to 250 μm.

In one embodiment, the hollow fiber membrane group may have a length of 5 cm to 100 cm, preferably 100 mm to 400 mm.

In one embodiment, the hollow fiber membrane group may have a diameter of 10 mm to 500 mm, preferably 35 mm to 100 mm.

In one embodiment, the source of liquid can be a water tank.

In another embodiment, the source of liquid may be water or other low concentration liquid that meets drinking standards and is connected to the inlet of the housing through a conduit.

In one embodiment, the hydrogen source can be a hydrogen tank.

In another embodiment, the hydrogen source can be a hydrogen generator.

In one embodiment, the liquid inlet is disposed at a top end of the casing, the liquid discharge port is disposed at a bottom end of the casing, and the air inlet is disposed at a sidewall of the casing.

In an embodiment, the air inlet is disposed at an upper portion of a sidewall of the housing.

In one embodiment, a pressure sensor is provided at the air inlet.

In one embodiment, a flow sensor is provided at the inlet of the housing.

Preferably, the pressure of the hydrogen flowing in the casing is greater than the pressure of the liquid flowing inside the hollow fiber membrane tube. And when the inlet pressure is less than the water pressure At the time, the hydrogen content of the effluent is lowered.

In one embodiment, the pressure of the hydrogen is between 1.5 and 1.7 times the pressure of the liquid.

In one embodiment, the pressure of the liquid is atmospheric.

Preferably, the inlet pressure of hydrogen at the inlet is 0.05 MPa to 0.6 MPa.

More preferably, the intake pressure of hydrogen gas at the intake port is 0.08 MPa to 0.3 MPa.

In another embodiment, the membrane pores of the hollow fiber membrane tube have a diameter of 1 nm to 1 μm.

Preferably, the diameter of the membrane pores of the hollow fiber membrane tube is 4 nm to 10 nm.

In one embodiment, the hollow fiber membrane group has a length of 5 cm to 100 cm and a diameter of 10 mm to 500 mm, and the hollow fiber membrane tube has a porosity of 30% to 70%.

In one embodiment, the hollow fiber membrane tube has a corrugated structure, or a transverse weave is added between the hollow fiber membrane tubes.

In one embodiment, the hollow fiber membrane tube has a circular or elliptical cross section.

In one embodiment, the hollow fiber membrane tube is made of a hydrophobic material doped with a hydrophilic material.

In another embodiment, the hollow fiber membrane tube is gas permeable or water permeable.

In another embodiment, the hollow fiber membrane tube is gas permeable and water impermeable.

In another embodiment, the hollow fiber membrane tube is made of a hydrophobic material.

In one embodiment, the hollow fiber membrane tube is made of an organic high molecular polymer.

In one embodiment, the hydrophobic material is selected from the group consisting of polyfluorene (PS), polydecylamine (PA), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polyether oxime (PES), polypropylene ( PP), one or more of polyvinylidene fluoride (PVDF), polyethylene (PE). The hydrophilic material is selected from a polymeric hydrophilic material having a large amount of hydrophilic groups such as polymethyl methacrylate (PHEMA), polyacrylamide (PAM), or polyvinylpyrrolidone (PVP). Preferably, the hydrophilic material is selected from the group consisting of polyvinylpyrrolidone (PVP) and the like.

In one embodiment, the hollow fiber membrane tube is composed of polyfluorene (PS), polydecylamine (PA), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polyether oxime (PES). Made of one or more.

In one embodiment, a pressure relief port is further disposed on a sidewall of the housing, and the pressure relief port is provided with a pressure relief device.

In one embodiment, the inlet end of the hollow fiber membrane group is fixedly coupled to the first end of the housing and each hollow fiber membrane tube has no gap between the hollow fiber membrane tubes at the inlet end, the hollow fiber membrane group An outlet end is fixedly coupled to the second end of the housing and each hollow fiber membrane tube has no gap between each other at the outlet end, and each hollow fiber membrane tube is between the inlet end and the outlet end The portions are spaced apart from each other to form a gap, so that hydrogen gas can flow in the gap.

In one embodiment, the hydrogen source is a hydrogen generator, and an outlet of the hydrogen generator is in communication with an inlet of the housing.

In one embodiment, the preparation device further includes a water tank provided with a water tank water inlet and a water tank water outlet, wherein the water tank water outlet is in communication with the liquid inlet of the casing, the water tank inlet and the liquid Source connected, or the water tank is flooded The port is connected to the liquid source via the first branch and communicates with the liquid discharge port of the housing via the second branch, and the first branch and the second branch are each provided with a valve.

In one embodiment, a pump or valve is provided between the water outlet of the water tank and the inlet of the housing. Preferably, the valve is a one-way valve.

In one embodiment, the preparation device is further provided with a third branch and a fourth branch, one end of the third branch is in communication with the liquid discharge port of the housing, and the other end of the third branch a first water intake port, and a valve is disposed on the third branch road before the first water intake port; and one end of the fourth branch road communicates with a liquid discharge port of the housing, the fourth The other end of the branch is a second water intake, and a heating device is provided on the fourth branch before the second water intake for heating the supersaturated hydrogen solution. Preferably, one end of the fourth branch that communicates with the liquid discharge port is in communication with the third branch.

In one embodiment, the housing and the hollow fiber membrane group together constitute a gas source mixer, the preparation device further comprising a water tank, the water tank is provided with a water tank water inlet and a water tank water outlet, wherein the water tank water outlet and the housing The inlet port is connected, and a valve is arranged on the pipeline between the water outlet and the liquid inlet, the water inlet is connected to the inlet of the casing via the sixth branch, and the fifth branch of the sixth branch is branched out. The liquid port is connected, and the fifth branch road and the sixth branch road are both provided with valves.

In one embodiment, a gas source purification device is provided between the gas source and the gas source mixer.

In another embodiment, the gas source purification device is a drying tube or a gas-liquid separation tank.

In one embodiment, a water source purification device is provided between the water source and the gas source mixer.

In another embodiment, the water purification device is an ultrafiltration membrane, a microfiltration membrane or an RO reverse osmosis membrane.

The invention also discloses a three-in-one gas-liquid mixing device, comprising a gas-liquid mixing device, the gas-liquid mixing device is composed of a shell and a hollow fiber membrane group, and further comprises a water source purifying device and a gas source purifying device, gas-liquid mixing device. The first inlet end of the device is connected to the gas source purifying device, and the inlet of the gas source purifying device is connected with hydrogen, and the second inlet end of the gas-liquid mixing device is connected with the water source purifying device, and the inlet of the water source purifying device is connected with the water source.

In one embodiment, the water source purification device comprises an ultrafiltration membrane.

In one embodiment, the gas source purification device comprises a drying tube.

In another embodiment, the gas source purifying device, the water source purifying device, and the gas-liquid mixer are connected in the same casing through a pipeline.

According to another aspect of the present invention, there is provided a method of producing a supersaturated hydrogen solution, the method comprising the steps of: A, providing a membrane element; and B, causing a liquid to flow on a first side of the membrane element while Hydrogen is caused to enter the liquid flowing in the first side of the membrane element from the other side of the membrane element via the membrane pore of the membrane element and to mix with the liquid.

In one embodiment, the membrane element is selected from one or more of the group consisting of hollow fiber, plate and frame, roll, folded, and tubular membrane elements.

Preferably, the pressure of the hydrogen is greater than the pressure of the liquid

Preferably, the pressure of the hydrogen gas is 0.05 MPa to 0.6 MPa.

In one embodiment, the membrane element is a hollow fiber membrane group comprising a plurality of hollow fiber membrane tubes, a liquid flowing inside the hollow fiber membrane tube while allowing hydrogen gas to pass through the hollow fiber membrane The membrane pore of the tube enters the hollow fiber The inside of the tube is mixed with the liquid.

Preferably, the pressure of the hydrogen gas is greater than the pressure of the liquid flowing inside the hollow fiber membrane tube. When the pressure at the inlet end is less than the water pressure, the hydrogen content of the effluent decreases.

In one embodiment, the membrane element is a hollow fiber membrane group, and the hollow fiber membrane group comprises a plurality of hollow fiber membrane tubes having a length of 5 cm to 100 cm and a diameter of 10 mm to 500 mm. The diameter of the membrane pores of the hollow fiber membrane tube is 1 nm to 1 μm, and the porosity of the hollow fiber membrane tube is 30% to 70%.

In one embodiment, the preparation method further includes providing a hydrogen generator, starting the hydrogen generator before step B, and raising the pressure of the outlet end of the hydrogen generator to a nominal value.

In one embodiment, the membrane element is a hollow fiber membrane group, the hollow fiber membrane group includes a plurality of hollow fiber membrane tubes, and the preparation method further comprises providing a casing, the casing being provided with a liquid source a liquid inlet, an air inlet for communicating with a hydrogen source, and a liquid discharge port, wherein the hollow fiber membrane group is housed in the casing, and an inlet end of the hollow fiber membrane group and the liquid inlet Connected so that liquid can flow inside the hollow fiber membrane tube, hydrogen from the hydrogen source enters the interior of the housing via the gas inlet, and then flows into the membrane through the membrane pore of the hollow fiber membrane tube The hollow fiber membrane tube is internally and mixed with a liquid, and an outlet end of the hollow fiber membrane group is in communication with the liquid discharge port.

In one embodiment, the liquid flow rate of the liquid discharge port of the housing is 0.200-2 L/min.

The hydrogen solution prepared according to the present invention has the following characteristics: Does not change the raw material water has the pH; does not change the raw water hardness (calcium, magnesium plasma concentration); the highest content of hydrogen in room temperature water ≧ 1.8mg / L; redox potential ORP ≦ -1000mv (WT20 ° C).

1‧‧‧Water tank

2‧‧‧Flow sensor

3‧‧‧ pump or valve

4‧‧‧Shell

5‧‧‧ check valve

6‧‧‧ check valve

24‧‧‧ Pressure Sensor

41‧‧‧ first end

42‧‧‧ inlet port

43‧‧‧Draining port

44‧‧‧air inlet

45‧‧‧pressure relief

7‧‧‧ heating device

8‧‧‧ check valve

9‧‧‧ check valve

10‧‧‧ Hydrogen generator

10a‧‧‧ outlet

11‧‧‧First road

12‧‧‧Second road

13‧‧‧ Third Road

14‧‧‧fourth road

15‧‧‧Water tank outlet

16‧‧‧Water tank inlet

17‧‧‧pipe

18‧‧‧Hollow fiber membrane group

19‧‧‧ hollow fiber membrane tube

20‧‧‧ entrance end

21‧‧‧ gap

22‧‧‧Binder

23‧‧‧export end

46‧‧‧ side wall

47‧‧‧ second end

61‧‧‧check valve

100‧‧‧Preparation device for supersaturated hydrogen solution

171‧‧‧ pipeline

172‧‧‧pipe

173‧‧‧ Fifth Road

174‧‧‧ sixth road

191‧‧‧ film hole

401‧‧‧3 in 1 mixer

402‧‧‧Drying tube

403‧‧‧UF filter

430‧‧‧ pipeline

440‧‧‧pipe

451‧‧‧export end

452‧‧‧ first import end

453‧‧‧second import end

Other features and effects of the present invention will be apparent from the following description of the drawings. FIG. 1 is a schematic diagram showing the system structure of the apparatus for preparing a supersaturated nanobubble hydrogen solution of the present invention; A schematic structural view of a gas-liquid mixer in a preparation apparatus, partially cut away to show an internal structure; FIG. 3 is an enlarged view of a portion A of FIG. 2; and FIG. 4 is a schematic structural view of an embodiment of a hollow fiber membrane tube, wherein FIG. 5 is a schematic view showing the system structure of a device for preparing a supersaturated nanobubble hydrogen solution in another embodiment; FIG. 6 is a schematic view showing the connection of a three-in-one gas-liquid mixer in another embodiment; 7 is a schematic structural view of a three-in-one gas-liquid mixer in another embodiment.

The preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be understood that the embodiments shown in the drawings are not intended to limit the scope of the invention The essence of the technical plan.

Name explanation

Supersaturated gas solution: Herein, the supersaturated gas solution is a mixture of a gas and a liquid. Here, the gas may be hydrogen, oxygen, nitrogen carbon dioxide or air, etc., and the liquid includes water, juice, and the like. When the gas is hydrogen, it is called a supersaturated hydrogen solution. The manner in which the gas is bound to the liquid is typically that the gas is present in the liquid in the form of nano or micronized bubbles. Supersaturation means that the mass concentration of the gas in the liquid is greater than the mass saturation concentration of the various gases at normal temperature and pressure.

Porosity Definition: The porosity of a material is the percentage of the pore volume in the material to the total volume of the material in its natural state, which is denoted by P. The calculation formula of the porosity P is: Where P is the porosity of the material, %; V ₀ is the volume of the material in the natural state, or apparent volume, cm ³ or m ³ ; ρ ₀ is the apparent density of the material, g / cm ³ or kg / m ³ ; V is the absolute compact volume of the material, cm ³ or m ³ ; ρ is the material density, g/cm ³ or kg/m ³ .

In the specific embodiments below, it will be described mainly based on a hollow fiber membrane group. It should be understood that the working principle of the present invention is that liquid flows on the first side of the membrane element, while gas passes from the membrane element on the other side of the membrane element, typically the side opposite the first side. The membrane pores enter the liquid flowing in the first side of the membrane element and are mixed with the liquid to prepare a supersaturated gas (e.g., hydrogen) solution. Under this principle, the membrane element can be selected from one or more of hollow fiber, plate and frame, roll, folded and tubular membrane elements. When the membrane element is a hollow fiber membrane module, it is also referred to as a hollow fiber membrane group.

1 and 2 show a preparation apparatus 100 for a supersaturated hydrogen solution according to a first embodiment of the present invention. As shown in Figures 1 and 2, the preparation apparatus 100 includes a casing 4 and a hollow fiber membrane group 18 housed in the casing 4, and the casing 4 and the hollow fiber membrane group 18 together constitute a hollow fiber membrane group gas-liquid mixer (e.g. Figure 2). The housing 4 is provided with a liquid inlet port 42 communicating with a liquid source, a liquid discharge port 43, an air inlet port 44 for communicating with a hydrogen source, and a pressure relief port 45, wherein the liquid discharge port is for discharging the prepared supersaturated hydrogen gas. The solution, pressure relief port is used to drain excess hydrogen, as described in further detail below. In this embodiment, the liquid source is the water tank 1, and the hydrogen source is the hydrogen generator 10, and the gas outlet 10a of the hydrogen generator is connected to the inlet 44 of the casing 4 through a pipe. It should be understood that the liquid source may also be municipal domestic water or the like which is connected to the inlet of the casing through a pipe. The liquid may be water that meets drinking water standards, or other low-viscosity liquids that meet drinking standards other than water, such as carbonated beverages, tea beverages, coffee beverages, or alcoholic beverages. The hydrogen source may also be a hydrogen tank or the like.

The hollow fiber membrane group 18 includes a plurality of hollow fiber membrane tubes 19, typically 8,000-15,000 hollow fiber membrane tubes. All of the hollow fiber membrane tubes 19 are fixedly coupled together (for example, by bonding) to form the inlet end 20 of the hollow fiber membrane group, and each of the hollow fiber membrane tubes 19 has no gap between the inlet ends 20, that is, a tight connection. Together, water or other fluid cannot flow between adjacent hollow fiber tubes at the inlet end. The other ends of all of the hollow fiber membrane tubes are also fixedly joined together (for example by bonding) to form the outlet end 23 of the hollow fiber membrane group 18, and each hollow fiber membrane tube 19 has no gap between the outlet ends 23, i. They are tightly joined so that water or other fluids cannot flow between adjacent hollow fiber tubes to the outlet end. The hollow fiber membrane tube portions between the inlet end 20 and the outlet end 23 of the hollow fiber membrane group are spaced apart from each other, that is, there is a gap 21 between them, so that gas can be in the gap between the individual hollow fiber membrane tubes. Flowing in 21

The inlet end 20 of the hollow fiber membrane stack 18 is fixedly joined (e.g., bonded by an adhesive 22) to the first end 41 of the housing 4. Similarly, the outlet end 23 of the hollow fiber membrane stack is fixedly joined (e.g., bonded by an adhesive) to the second end 47 of the housing. The inlet end 20 of the hollow fiber membrane group 18 communicates with the liquid inlet port 42 so that liquid can flow inside the hollow fiber membrane tube. The outlet end 23 of the hollow fiber membrane group 18 is in communication with the liquid discharge port 43, so that the prepared supersaturated hydrogen solution can be discharged. When the preparation device 100 is in operation, hydrogen from the hydrogen generator 10 flows from the membrane pores 191 of the hollow fiber membrane tube 19 into the interior of the hollow fiber membrane tube and is mixed with the liquid, and the hydrogen gas exists in the liquid in the form of nano-sized bubbles, thereby forming super Saturated hydrogen solution.

Specifically, the preparation principle of the supersaturated hydrogen solution is “micro-pipe gas-liquid two-phase flow” method, and the micro-pipe gas-liquid two-phase flow method simultaneously controls gas and liquid flow, and disperses gas by shear force between liquid and gas. Small bubbles with uniform size, the micro-bubble generated by the gas-liquid two-phase flow method of the micro-pipe mainly relies on the shear force between the liquid and the gas, and the micro-bubble generated by the micro-bubble can be equal to or even smaller than the micro-pipe (the hollow fiber membrane wall) Small hole).

It should be noted that the inventors have found through research that different materials, membrane surface area, length, diameter, porosity and pore size of the membrane pores for the hollow fiber membrane tube group and the hollow fiber membrane tube are supersaturated for the final preparation. The hydrogen concentration of the hydrogen solution has a certain influence.

In one embodiment, the hollow fiber membrane group has a length of from 5 cm to 100 cm, preferably from 100 mm to 400 mm. The hollow fiber membrane group has a diameter of 10 mm to 500 mm, preferably 35 mm to 100 mm.

In one embodiment, the hollow fiber membrane tube has a wall thickness of 20-50 μm.

In one embodiment, the inner diameter of the hollow fiber membrane is 40 μm to 400 μm. The grounding is 150-250 μm.

In one embodiment, the diameter of the membrane pores of the hollow fiber membrane tube is from 1 nm to 1 μm, and preferably, the diameter of the membrane pores of the hollow fiber membrane tube is from 4 nm to 10 nm.

In one embodiment, the hollow fiber membrane tube has a porosity of from 30% to 70%, preferably from 40% to 50%.

In addition, in order to avoid a large number (eight thousand to 15,000) of interfiber membrane adhesions in the hollow fiber membrane group, the hollow fiber membrane tube may have a corrugated structure, or a transverse weave may be added between the hollow fiber membrane tubes.

The hollow fiber membrane tube can have any suitable cross-sectional shape. Preferably, the hollow fiber membrane tube has a circular or elliptical cross section.

The hollow fiber membrane tube can be made of any suitable material. Preferably, the hollow fiber membrane tube is made of a hydrophilic-hydrophobic amphoteric membrane material. Here, the hydrophilic-hydrophobic bis-membrane material refers to hydrophobicity such as polyfluorene (PS), polyamine (PA), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyether oxime (PES), and the like. A material mainly composed of a hydrophilic material such as polyvinylpyrrolidone (PVP) and having hydrophilic and hydrophobic characteristics. In one embodiment, the hollow fiber tube is gas permeable or permeable to water. In another embodiment, the hollow fiber tube is gas permeable and water impermeable. In another embodiment, the hollow fiber membrane tube is made of a hydrophobic material. In one embodiment, the hollow fiber membrane tube is made of an organic high molecular polymer. In one embodiment, the hollow fiber membrane is mainly composed of polyfluorene (PS), polydecylamine (PA), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) or polyether oxime (PES). Made of doped polyvinylpyrrolidone (PVP).

The housing is a columnar body which may be made of a material such as polycarbonate. The inlet port 42 is connected (e.g., by threading) to the first end 41 of the housing 4. The drain port 43 is connected (e.g., by threading) to the second end 47 of the housing 4. An air inlet 44 is disposed in the Side wall 46 of the housing. Specifically, the air inlet 44 is disposed at an upper portion of the side wall of the housing 4 and below the inlet end 20 of the hollow fiber tube stack to be in fluid communication with the gap 21 between the hollow fiber membrane tubes. The pressure relief port 45 is disposed at a lower portion of the side wall of the casing, and the pressure relief port 45 can be installed with a pressure relief device such as a pressure relief valve. When the pressure in the housing exceeds a predetermined threshold, for example, a value between 0.05 MPa and 0.6 MPa, the pressure relief device operates to reduce the pressure of the gas in the housing, ensure the normal operation of the preparation device 100, and enable a certain concentration to be prepared. Hydrogen solution.

A pressure sensor can be provided at the air inlet 44. A control device (not shown) can control the operation of the hydrogen generator based on the pressure detected by the pressure sensor. Similarly, a pressure sensor 24 can also be provided within the hydrogen generator. In order to make hydrogen more efficiently present in the liquid in the form of nano-sized bubbles, the pressure of the hydrogen flowing in the casing should be greater than the pressure of the liquid flowing inside the hollow fiber membrane tube. In one embodiment, the pressure of the liquid is at or near atmospheric pressure, and the inlet pressure of the inlet 44 is 0.05 MPa to 0.6 MPa.

A flow sensor (not shown) is disposed at the inlet port 42, or a flow sensor 2 is disposed on the line between the water tank and the inlet port of the housing for detecting the amount of liquid flowing into the hollow fiber membrane group. . A pump or valve 3 is also provided on the line between the water tank and the inlet for turning the liquid source on or off. Preferably, the valve is a one-way valve.

The water tank 1 is provided with a water tank water inlet 16 and a water tank water outlet 15, wherein the water tank water outlet 15 communicates with the liquid inlet 42 of the casing via a line 17. The water tank water inlet 16 is connected to the liquid source via the first branch 11 and communicates with the liquid discharge port 43 of the casing via the second branch 12, and the first branch and the second branch are respectively provided with one-way Valves 9 and 5. Alternatively, the water tank inlet 16 can be in direct communication with a source of liquid.

In the embodiment shown in FIG. 1, the preparation device 100 is further provided with a third branch. The road 13 and the fourth branch 14, the one end of the third branch 13 communicates with the liquid discharge port 43 of the casing, and the other end of the third branch is the first water intake port. A check valve 6 is provided on the third branch before the first water intake. One end of the fourth branch 14 is in communication with the liquid discharge port 43 of the casing, and the other end of the fourth branch is a second water intake port. The fourth branch is provided with a heating device 7 for heating the supersaturated hydrogen solution before the second water intake. A check valve 8 is also provided on the fourth branch before the second water intake. In the embodiment shown in FIG. 1, one end of the fourth branch 14 that communicates with the liquid discharge port 43 is in communication with the third branch 13. It should be understood that the fourth branch 14 can also be directly connected to the drain opening 43 by a separate line.

In a variant, since the hydrogen solution from the liquid discharge port of the casing is already a drinkable supersaturated hydrogen solution, the liquid discharge port of the casing can be directly connected to the water pipe or the valve, that is, the second branch is not provided. 12 and the fourth branch 14.

In a variant, only one of the second branch 12 and the fourth branch 14 may be provided.

In a variant, as described above, instead of providing a water tank, the inlet of the housing can be connected to other sources of liquid.

In the embodiment shown in FIG. 5, the water tank outlet 15 is in communication with the housing inlet port 42 via a line, the line 171 is provided with a pump or valve 3, and the pump or valve 3 is connected to the drain port 42 via a line 172, the tube A check valve 61 is disposed on the road 172, and the liquid discharge port 43 is connected to the check valve 5 and the heater 7, and then connected to the fifth branch 173, and the sixth branch 174. The sixth branch 174 is provided with a valve and the water inlet 16 Connected, the fifth branch 173 is in communication with the liquid outlet.

In another embodiment, the gas-liquid mixer is a three-in-one mixer 401. As shown in FIG. 6 and FIG. 7, the first inlet end 452 is connected to the hydrogen gas, the second inlet end 453 is connected to the water, and the outlet end 451 is discharged. The hydrogen-containing water, the three-in-one mixer 401 is connected to the hydrogen through the pipeline 430, the drying pipe 402 is disposed on the connecting pipe 430, and the three-in-one mixer 401 is passed through the pipeline. The 440 is connected to the water, and the UF filter 403 is disposed on the line 440.

In the supersaturated hydrogen solution preparation device of the present invention, the amount of supersaturated hydrogen water prepared is adjustable, for example, by using a vacuum fiber gas-liquid mixer with different specific surface areas or a plurality of small gas-liquid mixers in parallel, 0~100L/H can be realized. (Available in larger quantities) Instant preparation of supersaturated hydrogen water.

The key to the apparatus for preparing a supersaturated hydrogen solution of the present invention is to provide a hollow fiber membrane group including a plurality of hollow fiber membrane tubes, and then to cause a liquid to flow inside the hollow fiber membrane tube while allowing hydrogen gas to pass through the hollow fiber membrane tube The membrane pores enter the inside of the hollow fiber membrane tube and are mixed with a liquid, thereby preparing a supersaturated hydrogen solution. Under the above principle method, the preparation device of various structural forms can be used to achieve the object of the present invention.

As an illustrative example, an example of preparing a supersaturated hydrogen solution under different conditions is listed below.

Example 1

15000 polyether 碸 hollow fiber membrane tubes having an inner diameter of 200 μm, a membrane wall thickness of 35 μm, a membrane pore size of 5-7 nm, and a porosity of 40% were packaged in a polycarbonate casing having an outer diameter of 32 mm and a length of 264 mm to form a single sheet. The hollow fiber membrane group gas-liquid mixer has a hollow fiber membrane group having a maximum diameter of about 37 mm and a total length of about 305 mm. The hydrogen generator is connected to the air inlet, the air outlet is connected to the safety valve, the liquid inlet is connected to the drinking water through the pipeline, and the pump outlet is directly connected to the water. The inlet pressure is maintained at 0.18 MPa, the water pressure is normal pressure (about 0.1 MPa), the effluent flow rate is stable at 760 ml/min, the influent hydrogen content is 0, and the effluent hydrogen content is 5.9 ppm, which is 20 ° C, 1 standard atmospheric pressure of hydrogen. The saturation concentration is 3.69 times. The obtained hydrogen aqueous solution contains more than 2*10 ⁹ nanometer bubbles per milliliter, and the hydrogen gas bubbles are 95% below 50 nm, and the power consumption of the whole machine is less than 20 watts. When the pressure at the inlet end is less than the water pressure, the hydrogen content of the effluent decreases.

Example 2

The equipment is the same as the example 1, the inlet end pressure is maintained at 0.18 MPa, the water pressure is normal pressure (about 0.1 MPa), and the outlet water flow rate is greater than 900 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 3.6 ppm, the concentration is 20 ° C, and the hydrogen saturation is 2.25 times at 1 standard atmospheric pressure.

Conclusion: The concentration of the saturated solution prepared by the smaller inlet pressure and higher flow rate is significantly lower than the larger inlet pressure and lower flow rate.

Example 3

The equipment is the same as the example 1, the inlet end pressure is maintained at 0.10 MPa, the water pressure is normal pressure, and the outlet water flow rate is greater than 1200 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 2.5 ppm, the concentration is 20 ° C, and the hydrogen saturation is 1.56 times at 1 standard atmospheric pressure.

Conclusion: The concentration of saturated solution prepared with a smaller inlet pressure and a higher effluent flow rate is significantly lower than the larger inlet pressure and lower effluent flow rate.

Example 3’

The equipment is the same as the example 1, the inlet end pressure is maintained at 0.10 MPa, the water pressure is normal pressure, and the outlet water flow rate is 200 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 4.3 ppm, the concentration is 20 ° C, and the hydrogen saturation is 1.69 times at 1 standard atmosphere.

Conclusion: The concentration of saturated solution prepared by the higher flow rate of lower effluent flow rate is significantly higher.

Example 4

The equipment is the same as in the example 1. The inlet pressure is maintained at 0.10 MPa, the water pressure is normal pressure, and the outlet water flow rate is greater than 1500 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 2.1 ppm, the concentration is 20 ° C, and the hydrogen saturation is 1.31 times at 1 standard atmospheric pressure.

Conclusion: Smaller inlets relative to larger inlet pressures and lower outlet flow rates The concentration of the saturated solution prepared by the gas pressure and the higher water flow rate is significantly reduced.

Example 5

The equipment is the same as the example 1, the inlet end pressure is maintained at 0.08 MPa, the water pressure is normal pressure, and the outlet water flow rate is greater than 1200 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 1.8 ppm, the concentration is 20 ° C, and the hydrogen saturation is 1.13 times at 1 standard atmospheric pressure.

Conclusion: Under the same equipment and the same parameters, the higher the pressure at the inlet end, the higher the hydrogen content. Under the same equipment and the same parameters, the lower the water flow rate, the higher the hydrogen content.

Example 6

8000 polyether 碸 hollow fiber membrane tubes with an inner diameter of 300 μm, a membrane wall thickness of 45 μm and a membrane pore size of 40 nm were packaged in a polycarbonate shell with an outer diameter of 75 mm and a length of 280 mm to form a single-group hollow fiber membrane group. Device. The hydrogen generator is connected at the inlet end, the outlet port is connected with a safety valve, the inlet end is connected to the drinking bucket through the pipeline, and the drain port is directly drained. The inlet end pressure is maintained at 0.1 MPa, the water pressure is normal pressure, the effluent flow rate is stabilized at 2 L/min, the influent hydrogen content is 0, and the effluent hydrogen content is 0.9 ppm.

Conclusion: Compared with the small pore size (5-7 nm in Example 1) hollow fiber membrane, 5.9 ppm was prepared, and the concentration of the saturated solution prepared by the large pore membrane was significantly reduced.

Example 7

The equipment is the same as the first example. The same material with the pore size of the membrane is 30 nm. The other parameters are the same as in the example 1. The pressure at the inlet end is maintained at 0.18 MPa, the water pressure is normal pressure, the flow rate of the water is stable at 760 ml/min, and the hydrogen content of the influent is 0. The effluent hydrogen content is 2.2 ppm.

Conclusion: The larger the membrane pore size, the lower the hydrogen concentration in the preparation of saturated hydrogen water.

Example 8

The equipment is the same as the first example, and the same material with the porosity of 30% is selected. The other parameters are the same as in the example 1. The inlet pressure is maintained at 0.18 MPa, the water pressure is normal pressure, the water flow rate is stable at 760 ml/min, and the influent hydrogen content is 0. The effluent hydrogen content is 2.9ppm.

Conclusion: The lower the porosity of the membrane, the lower the hydrogen concentration in the preparation of saturated hydrogen.

Example 8’

The equipment is the same as the first example, and the same material with the porosity of 70% is selected. The other parameters are the same as in the example 1. The pressure at the inlet end is maintained at 0.18 MPa, the water pressure is normal pressure, the water flow rate is stable at 760 ml/min, and the influent hydrogen content is 0. The effluent hydrogen content is 6.9ppm.

Conclusion: The higher the porosity of the membrane, the higher the hydrogen concentration in the preparation of saturated hydrogen.

Example 9

15,000 polyether 碸 hollow fiber membrane tubes (no hydrophilic material added to the membrane material) having an inner diameter of 200 μm, a membrane wall thickness of 35 μm, and a membrane pore size of 5-7 nm were encapsulated in a polycarbonate casing having an outer diameter of 37 mm and a length of 305 mm. , constitute a single group of hollow fiber membrane group gas-liquid mixer. The hydrogen generator is connected at the inlet end, the outlet port is connected with a safety valve, the inlet end is connected to the drinking bucket through the pipeline, and the drain port is directly drained. The inlet pressure is maintained at 0.18 MPa, the water pressure is normal pressure, the effluent flow rate is stable at 760 ml/min, the influent hydrogen content is 0, the effluent hydrogen content is 3.9 ppm, and the hydrogen saturation concentration is 3.69 at 20 ° C and 1 standard atmospheric pressure. Times.

Conclusion: Compared with the hollow fiber membrane of the hydrophobic and hydrophobic membrane, 5.9ppm was prepared, and the concentration of the saturated solution prepared by the pure hydrophobic membrane was significantly reduced.

Herein, the titration method of the hydrogen concentration is titrated by the dissolved hydrogen concentration determining reagent of No. 4511361 of MiZ Corporation of Japan, and will not be described in detail herein.

The preparation device and the preparation method of the supersaturated nanobubble hydrogen solution of the invention have the following advantages: 1. The supersaturated nanobubble hydrogen solution can be prepared immediately without preparing the waiting time; 2. The hydrogen concentration range of the solution is 1.2 ppm~ 6ppm; 3. The nanometer scale distribution of hydrogen bubbles is 95% below 50nm; 4. More than 2*10 ⁹ nanometer bubbles per milliliter of solution; 5. The dissolved gas efficiency is super high, and the effective dissolution rate of hydrogen exceeds 80%; 6. The power consumption of the whole machine is low.

Example 10

The equipment is the same as in Example 3. The inlet pressure is maintained at 0.3 MP, the water pressure is normal pressure, and the outlet water flow rate is greater than 1200 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 4.8 ppm, the concentration is 20 ° C, and the hydrogen saturation is 3 times at 1 standard atmospheric pressure.

Conclusion: The concentration of saturated solution prepared by the larger inlet pressure is significantly higher than that of the smaller inlet pressure.

Example 11

The equipment is the same as in Example 3. The inlet end pressure is maintained at 0.5 MP, the water pressure is normal pressure, and the outlet water flow rate is greater than 1200 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 5.6 ppm, the concentration is 20 ° C, and the hydrogen saturation is 3.54 times at 1 standard atmospheric pressure.

Conclusion: The concentration of saturated solution prepared by the larger inlet pressure is significantly higher than that of the smaller inlet pressure.

Example 12

The hollow fiber membrane component device is the same as in the first example. A valve (61) is added between the pump (3) and the gas-liquid mixer. The valve 61 may be a one-way valve or a reverse-mounted solenoid valve, as shown in FIG. The specific connection relationship is: the water tank outlet 15 communicates with the casing inlet port 42 via the pipeline, the pipeline 171 is provided with a pump or valve 3, and the pump or valve 3 is connected to the drain port 42 through the pipeline 172, and the pipeline 172 is disposed. Check valve 61, drain port 43 connected to check valve 5 Lines 174 and 173 are connected to the heater 7, and a valve is provided on the line 174 and communicates with the water inlet 16 which is provided with a water valve. The gas source and gas-liquid mixer are also connected to a gas source purifying device, which in the present embodiment is a drying tube, and the water source and the gas-liquid mixer are connected to a water source purifying device, which in this embodiment is an ultrafiltration membrane. The gas source purifying device, the water source purifying device, and the gas-liquid mixer may also be connected in the same casing. The inlet pressure is maintained at 0.18 MPa, the water pressure is normal pressure (about 0.1 MPa), and the outlet water flow rate is greater than 900 ml/min. The influent hydrogen content is 0, the effluent hydrogen content is 3.6 ppm, the concentration is 20 ° C, and the hydrogen saturation is 2.25 times at 1 standard atmospheric pressure.

Conclusion: Compared with the structure of Fig. 1, the time from the rise of the inlet end pressure from 0 Mpa to 0.18 MPa is greatly shortened, and the pressure is gradually maintained unchanged with respect to the pressure gradually decreasing in Fig. 1. This change enhances system stability.

The preferred embodiments of the present invention have been described in detail hereinabove, and it is understood that various modifications and changes may be made by those skilled in the art. These equivalent forms are also within the scope defined by the scope of the appended claims.

1‧‧‧Water tank

2‧‧‧Flow sensor

3‧‧‧ pump or valve

4‧‧‧Shell

5‧‧‧ check valve

6‧‧‧ check valve

7‧‧‧ heating device

10a‧‧‧ outlet

11‧‧‧First road

12‧‧‧Second road

13‧‧‧ Third Road

14‧‧‧fourth road

15‧‧‧Water tank outlet

16‧‧‧Water tank inlet

8‧‧‧ check valve

9‧‧‧ check valve

10‧‧‧ Hydrogen generator

17‧‧‧pipe

24‧‧‧ Pressure Sensor

100‧‧‧Preparation device for supersaturated hydrogen solution

Claims (19)

A device (100) for preparing a supersaturated hydrogen solution, comprising: a casing (4) and a hollow fiber membrane group (18), wherein the casing (4) is provided with a liquid inlet (42) communicating with a liquid source, An air inlet (44) for communicating with a hydrogen source and a liquid discharge port (43), the hollow fiber membrane group (18) comprising a plurality of hollow fiber membrane tubes (19) and housed in the housing (4) The inlet end (20) of the hollow fiber membrane group (18) is in communication with the liquid inlet (42) such that liquid can flow inside the hollow fiber membrane tube (19) and from the hydrogen source Hydrogen gas can flow from the membrane pores (191) of the hollow fiber membrane tube (19) into the interior of the hollow fiber membrane tube (19) and mix with the liquid, and the outlet end of the hollow fiber membrane group (18) ( 23) is in communication with the liquid discharge port (43). The preparation apparatus according to claim 1, wherein a pressure of hydrogen flowing in the casing (4) is greater than a pressure of a liquid flowing inside the hollow fiber membrane tube (19). The preparation apparatus according to claim 1, wherein the inlet pressure of hydrogen gas at the intake port is 0.05 MPa to 0.6 MPa. The preparation apparatus according to claim 1, wherein the hollow fiber membrane group (18) has a length of 5 cm to 100 cm and a diameter of 10 mm to 500 mm, and the hollow fiber membrane tube (19) has a porosity of 30%. -70%. The preparation apparatus according to claim 1, wherein the hollow fiber membrane tube (19) is made of a hydrophobic material or a hydrophobic material doped with a hydrophilic material. The preparation device according to claim 1, wherein the side wall (46) of the casing (4) is further provided with a pressure relief port (45), and the pressure relief port is provided with a pressure relief device. The preparation device according to claim 1, wherein the inlet end (20) of the hollow fiber membrane group (18) is fixedly coupled to the first end (41) of the housing and each hollow fiber membrane tube (19) There is no gap between the inlet ends (20), the outlet end (23) of the hollow fiber membrane group is fixedly connected to the second end (47) of the casing and each hollow fiber membrane tube (19) There is no gap between the outlet ends (23), and portions of the respective hollow fiber membrane tubes (19) between the inlet end (20) and the outlet end (23) are spaced apart from each other to form a gap. (21), whereby hydrogen gas can flow in the gap (21). The preparation device according to claim 1, wherein the hydrogen source is a hydrogen generator (10), an air outlet (10a) of the hydrogen generator (10) and an air inlet of the casing (4) (44) Connected. The preparation device according to claim 1, wherein the preparation device (100) further comprises a water tank (1), the water tank (1) is provided with a water tank water inlet (16) and a water tank water outlet (15), wherein The water tank outlet (150) is in communication with a liquid inlet (42) of the casing (4), the tank inlet (16) is in communication with a liquid source, or the tank inlet (16) is via a first branch The road (11) is connected to the liquid source and communicates with the liquid discharge port (43) of the casing (4) via the second branch (12), and the first branch (11) and the second branch Valves (9, 5) are provided on the road (12). The preparation device according to claim 1, wherein the casing (4) and the hollow fiber membrane group (18) together constitute a gas source mixer, the preparation device (100) further comprising a water tank (1), The water tank (1) is provided with a water tank water inlet (16) and a water tank water outlet (15), wherein the water tank water outlet (15) and the casing (4) are advanced The liquid port (42) is connected, and a valve (61) is disposed on the pipeline between the water outlet (15) and the liquid inlet (42), and the water inlet (16) passes through the sixth branch and the casing (4) The liquid inlet (42) is in communication, and the fifth branch (173) of the sixth branch (174) is connected to the liquid outlet, the fifth branch (173) and the sixth branch (174) There are valves on the top. The preparation apparatus according to claim 1, wherein a gas source purification device is provided between the gas source and the gas source mixer. The preparation apparatus according to claim 1, wherein a water source purification device is provided between the water source and the gas source mixer. A three-in-one gas-liquid mixing device comprising: a gas-liquid mixing device (401), the gas-liquid mixing device (401) comprising a casing (4) and a hollow fiber membrane group in the preparation device according to claim 1 (18) The composition further includes a water source purifying device (403) and a gas source purifying device (402). The first inlet end (452) of the gas-liquid mixing device (401) is connected to the gas source purifying device (402), and the gas source purifying device The inlet of (402) is connected to the hydrogen gas, and the second inlet end (453) of the gas-liquid mixing device (401) is connected to the water source purifying device (403), and the inlet of the water source purifying device (403) is connected to the water source. A method of preparing a supersaturated hydrogen solution comprising the steps of: A, providing a membrane element; and B, flowing a liquid on a first side of the membrane element while allowing hydrogen gas from the other side of the membrane element via the The membrane aperture of the membrane element enters and mixes with the liquid flowing in the first side of the membrane element. The production method according to claim 14, wherein the pressure of the hydrogen gas is greater than the pressure of the liquid. The preparation method according to claim 14, wherein the pressure of the hydrogen gas is 0.05 MPa to 0.6 MPa. The preparation method according to claim 14, wherein the membrane element is a hollow fiber membrane group (18), the hollow fiber membrane group (18) comprises a plurality of hollow fiber membrane tubes (19), and a liquid is in the hollow The inside of the fiber membrane tube (19) flows while allowing hydrogen gas to enter the inside of the hollow fiber membrane tube (19) via the membrane pore (191) of the hollow fiber membrane tube (19) and to be mixed with the liquid. The production method according to claim 14, wherein the preparation method further comprises providing a hydrogen generator, starting the hydrogen generator before the step B, and raising the pressure of the gas outlet end of the hydrogen generator to a rated value. . The preparation method according to claim 14, wherein the preparation method further comprises providing a casing provided with a liquid inlet connected to the liquid source, an air inlet for communicating with the hydrogen source, and a row a liquid port, wherein the hollow fiber membrane group is housed in the casing, and an inlet end of the hollow fiber membrane group is in communication with the liquid inlet port so that liquid can flow inside the hollow fiber membrane tube, The hydrogen gas of the hydrogen source enters the inside of the casing via the gas inlet, then flows into the hollow fiber membrane tube through the membrane pore of the hollow fiber membrane tube and is mixed with the liquid, and the hollow fiber membrane group The outlet end is in communication with the liquid discharge port.