Preparation method of high-desalination and high-boron-removal seawater desalination reverse osmosis membrane element

Abstract

The invention relates to the technical field of reverse osmosis membrane preparation, in particular to a preparation method of a high-desalination and high-boron-removal seawater desalination reverse osmosis membrane element, which is characterized in that a porous base membrane and a conventional part are conventionally rolled to form a roll type base membrane element, the water inlet flow channel at one end is fully filled with an amine monomer-containing water phase solution, the water inlet flow channel is purged by first compressed gas after standing, then the water inlet flow channel at the same end is fully filled with an acyl chloride monomer-containing oil phase solution, and standing is performed again so as to generate an interfacial polymerization reaction on the surface of the porous base membrane; after the water inlet runner is purged by second compressed gas, the spiral-wound composite membrane element is obtained, and a finished product is obtained after rinsing. Compared with a conventional method of firstly performing interfacial polymerization and then performing rinsing and rolling, the method disclosed by the invention can solve the technical problem that the desalination rate and the boron removal rate are reduced due to the fact that a polyamide desalination layer on the surface of the membrane is damaged in the rinsing and rolling process and the rolling process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of reverse osmosis membrane preparation, and particularly relates to a preparation method of a high-desalination and high-deboron seawater desalination reverse osmosis membrane element. BACKGROUND

[0002] Seawater desalination reverse osmosis membranes are widely used in seawater desalination and concentration of high-concentration materials or brine. Because the salt concentration of the inlet water is high (TDS value is 5000-50000 ppm) and the operation pressure is high (greater than 30 kg), and the desalination rate and the deboronization rate are extremely high, the production process has very high requirements for the control of micro-scale defects. Micron-level defects can significantly reduce the desalination rate and the deboronization rate.

[0003] A conventional seawater desalination reverse osmosis membrane sheet is a three-layer structure, including a polyester non-woven fabric reinforcing layer at the bottom, a polysulfone porous support layer in the middle, and a polyamide desalination layer at the top. The polyester non-woven fabric reinforcing layer and the polysulfone porous support layer constitute a porous base membrane, and the desalination layer above the porous base membrane is prepared by interfacial polymerization of an aqueous solution containing m-phenylenediamine and an oil phase solution containing trimesoyl chloride on the surface of the polysulfone porous base membrane. The residual unreacted substances in the newly prepared membrane sheet are removed by multi-stage rinsing, and then the membrane sheet is wound. The membrane sheet rinsing process is usually carried out in a water tank filled with pure water or chemical drugs, and the cleaning with a certain residence time is completed by repeatedly rolling in the tank. A series of rollers are needed for a high-speed membrane sheet production line to ensure the tension and stability of the production line, including the membrane sheet rinsing link and the membrane sheet winding link. The front roller directly contacts the polyamide desalination layer of the membrane surface, and repeated contact with the membrane surface will increase the damage of the polyamide desalination layer, resulting in a decrease in the desalination rate and the deboronization rate of the membrane sheet.

[0004] The membrane sheet is usually wound into a roll-type membrane element for use. The element structure is composed of a membrane sheet, a product water flow channel cloth, an inlet water grid, a product water center pipe and an end cover. The quality of the membrane sheet directly determines the separation performance of the membrane element. During the winding process of the element, the surface of the membrane sheet contacts and slides with the rough inlet water grid, which can cause scratches on the surface of the polyamide desalination layer, thereby reducing the desalination rate and the deboronization rate of the membrane element. SUMMARY

[0005] In order to solve the technical problems of the desalination rate and the boron removal rate caused by the damage of the polyamide desalination layer on the surface of the membrane during the rinsing-off roller process and the rolling process, the application provides a preparation method of a high desalination and high boron removal seawater desalination reverse osmosis membrane element.Compared with the conventional interface polymerization and then rinsing and rolling, the method of the application is to roll the porous base film to form a rolled membrane element, and then make the aqueous solution containing amine monomers and the oil phase solution containing amine reactive substances pass through the rolled base film element in sequence to cause the interface polymerization reaction on the surface of the porous base film, and then rinse, which can solve the technical problems of the desalination rate and the boron removal rate caused by the damage of the polyamide desalination layer on the surface of the membrane during the rinsing-off roller process and the rolling process.

[0006] In order to achieve the above purpose, the application is realized by the following technical scheme:

[0007] The preparation method of the high desalination and high boron removal seawater desalination reverse osmosis membrane element comprises the following steps:

[0008] S1, roll the porous base film and the conventional components to form a rolled base film element, the rolled base film element has at least one water inlet channel, fill the water inlet channel of one end with the aqueous solution containing amine monomers, after standing, blow the water inlet channel with the first compressed gas, after blowing until there is no liquid on the membrane surface, fill the water inlet channel of the same end with the oil phase solution containing acyl chloride monomers, stand again to cause the interface polymerization reaction on the surface of the porous base film, blow the water inlet channel with the second compressed gas, and obtain a rolled composite membrane element after blowing until there is no liquid on the membrane surface;

[0009] S2, rinse the rolled composite membrane element to obtain a high desalination and high boron removal seawater desalination reverse osmosis membrane element.

[0010] Further, the porous base film is a single-layer structure or a multi-layer structure;

[0011] The material of the single-layer structure is selected from one or more of polyethylene, polypropylene, polysulfone, sulfonated polysulfone, polyether sulfone, polyacrylonitrile, polyimide, polyamide, and polyvinylidene fluoride;

[0012] The multi-layer structure is a polyester non-woven fabric as a bottom layer and a support layer provided on the surface thereof, and the material of the support layer is one or more of polyethylene, polypropylene, polysulfone, sulfonated polysulfone, polyether sulfone, polyacrylonitrile, polyimide, polyamide, and polyvinylidene fluoride;

[0013] The surface pore size of the porous base film is 5 nanometers to 10 microns.

[0014] Further, the aqueous solution of the amine-containing monomer has a concentration of 0.5wt%-10wt%, the amine-containing monomer is selected from one or more of piperazine, m-phenylenediamine, tris (benzenetriyl) amine, polyethylenimine, triethylenetetramine, tetraethylenepentamine, 1, 3, 5-triaminobenzene, and the solvent in the aqueous solution is water;

[0015] Further, the oil phase solution of the acyl chloride-containing monomer has a concentration of 0.05wt%-1wt%, the acyl chloride-containing monomer is selected from one or more of benzene tricarboxylic acid chloride, p-phenylenediacid chloride, m-phenylenediacid chloride, m-phenylenedisulfonic acid chloride, 1, 3, 6-naphthalene trisulfonic acid chloride, and the solvent in the oil phase solution is a solvent capable of dissolving the acyl chloride monomer but not miscible with water and having a boiling point lower than 150℃, such as ethylcyclohexane, n-hexane, cyclohexane, Isopar E, etc.

[0016] Further, the standing time after filling the aqueous solution is 10 seconds to 30 minutes; the standing time after filling the oil phase solution is 1 second to 5 minutes.

[0017] Further, the first compressed gas and the second compressed gas are each independently selected from one of air, nitrogen, argon, and helium; the temperature of the first compressed gas is 10-70℃; the temperature of the second compressed gas is in the range of 30-90℃.

[0018] Further, the rinsing process is to sequentially introduce pure water, sodium hypochlorite aqueous solution, and sodium bisulfite aqueous solution into the water inlet channel at either end.

[0019] Further, the temperature of the introduced pure water is 0-100℃, the time of the introduction is 5 seconds to 10 minutes, and the pressure of the introduction is 0-60 kg;

[0020] The concentration of the sodium hypochlorite aqueous solution is 10-5000mg / L, the temperature is 10-40℃, the time of the introduction is 5 seconds to 10 minutes, and the pressure is 0-30 kg;

[0021] The concentration of the sodium bisulfite aqueous solution is 0.1wt%-10wt%, the temperature is 10-100℃, the time of the introduction is 5 seconds to 10 minutes, and the pressure is 0-30 kg.

[0022] Beneficial technical effects: the present application first rolls the porous base film to form a roll type base film element, then carries out interfacial polymerization on the roll type base film element to form a polyamide desalination layer, then rinses, and finally obtains the finished product reverse osmosis membrane element; in the present application, the membrane sheet does not need to be rinsed by passing through the roller, so that damage to the polyamide desalination layer during the passing process can be avoided, and the boron removal rate and desalination rate of the composite membrane sheet are ensured; and during the rolling process of the membrane element, the water inlet grid does not displace and scratch the polyamide desalination layer, so that damage to the desalination layer during the rolling process is avoided, and the boron removal rate and desalination rate of the composite membrane sheet are ensured; the production line omits the membrane sheet rinsing, membrane sheet moisturizing and drying links, reduces the equipment investment and production energy consumption of the production line, and reduces the process links and their influence on the stability of the product. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a process flow diagram of the present application. DETAILED DESCRIPTION

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application and the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative, but not as any limitation on the present application and its application or use. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0025] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present application. Techniques, methods known to those of ordinary skill in the relevant art can not be discussed in detail, but should be considered as part of the specification where appropriate. In all examples shown and discussed herein, any specific value should be interpreted as merely exemplary, and not as a limitation. Therefore, other examples of exemplary embodiments can have different values. It should be noted that, for example, values expressed as "in the range of a-b", "between a-b", do not include the end point values a and b; values expressed as "a-b", "is a-b", "a-b" include the end point values a and b.

[0026] In addition, it should be noted that the use of the words "first", "second", etc. to describe the compressed gas is only for the convenience of distinguishing the gas used in each step, and the above words have no special meaning unless otherwise stated, and therefore cannot be understood as limiting the scope of protection of the present application.

[0027] The experimental methods in the following embodiments not specified in the specific conditions are generally determined according to the national standard; if there is no corresponding national standard, they are carried out according to the general standard requirements or general methods.

[0028] The reverse osmosis membrane element structure is not different from the conventional one, and the conventional techniques are described in CN109715274A or CN102245283A, etc.

[0029] Embodiment 1

[0030] The preparation method of the high desalination and high boron removal reverse osmosis membrane element for seawater desalination comprises the following steps:

[0031] S1, a polysulfone porous base film with a thickness of 150 microns (surface pore size 10 nm, two-layer structure, bottom layer is polyester non-woven fabric, and upper layer is polysulfone porous film) is rolled into a roll type base film element with 26 membrane bags, and the membrane area is 37.2m 2 ;

[0032] The roll type base film element has water inlet channels at both ends. The water inlet channel at one end is filled with a water solution containing 3wt% m-phenylenediamine (filling operation: the element is erected, the liquid is injected from the bottom end, and the water phase solution flows out from the top end), and after standing for 30 seconds, the solution in the water inlet channel is completely blown off with 25℃ compressed air, and after blowing until there is no liquid on the membrane surface, the water inlet channel at the same end is filled with an oil phase solution containing 0.2wt% trimesoyl chloride (the solvent is ethylcyclohexane) (filling operation is the same as above), and after standing for 1 minute to generate an interfacial polymerization reaction on the surface of the porous base film, the solution in the water inlet channel is completely blown off with 40℃ compressed air, and after blowing until there is no liquid on the membrane surface, a roll type composite membrane element is obtained;

[0033] S2, pure water (3kg pressure) at 40℃ is introduced into the water inlet channel of the roll type composite membrane element (3kg pressure) for 10 minutes, then room temperature 500mg / L sodium hypochlorite aqueous solution (3kg pressure) is introduced for 2 minutes, and finally room temperature 1wt% sodium bisulfite aqueous solution (3kg pressure) is introduced for 2 minutes, and finally the finished product high desalination and high boron removal reverse osmosis membrane element for seawater desalination is obtained. Blow until there is no liquid on the membrane surface

[0034] Embodiment 2

[0035] The preparation method of the high desalination and high boron removal reverse osmosis membrane element for seawater desalination comprises the following steps:

[0036] S1, a polysulfone porous base film with a thickness of 150 microns (surface pore size 40 nm, two-layer structure, bottom layer is polyester non-woven fabric, and upper layer is polysulfone porous film) is rolled into a roll type base film element with 26 membrane bags, and the membrane area is 37.2m 2 ;

[0037] The roll type base membrane element has water inlet channels at both ends. The water inlet channel at one end is filled with a water solution containing 3wt% m-phenylenediamine (filling operation: the element is erected, the liquid is injected from the bottom end until the water phase solution flows out from the top end), after standing for 30 seconds, the solution in the water inlet channel is completely blown with compressed air at 25°C, until there is no liquid on the membrane surface, then the same water inlet channel at the same end is filled with an oil phase solution (the solvent is ethylcyclohexane) containing 0.1wt% trimesoyl chloride and 0.1wt% isophthaloyl chloride (filling operation as above), and then standing for 1 minute to generate an interfacial polymerization reaction on the surface of the porous base membrane, and the solution in the water inlet channel is completely blown with compressed air at 40°C, until there is no liquid on the membrane surface, to obtain a roll type composite membrane element;

[0038] S2, pure water at 40°C (3kg pressure) is introduced into the water inlet channel of either end of the roll type composite membrane element for 10 minutes, then room temperature 500mg / L sodium hypochlorite aqueous solution (3kg pressure) is introduced for 2 minutes, and finally room temperature 1wt% sodium bisulfite aqueous solution (3kg pressure) is introduced for 2 minutes, to obtain a finished high desalination and high boron removal seawater desalination reverse osmosis membrane element.

[0039] Example 3

[0040] A method for preparing a high desalination and high boron removal seawater desalination reverse osmosis membrane element, comprising the following steps:

[0041] S1, a polysulfone porous base membrane with a thickness of 140 microns (surface pore size 40nm, two-layer structure, the bottom layer is a polyester non-woven fabric, and the upper layer is a polysulfone porous membrane) is rolled into a roll type base membrane element with 26 membrane bags, and the membrane area is 37.2m 2 ;

[0042] The roll type base membrane element has water inlet channels at both ends. The water inlet channel at one end is filled with a water solution containing 3wt% m-phenylenediamine (water also contains 10wt% isopropyl alcohol; filling operation: the element is erected, the liquid is injected from the bottom end until the water phase solution flows out from the top end), after standing for 30 seconds, the solution in the water inlet channel is completely blown with compressed air at 25°C, until there is no liquid on the membrane surface, then the same water inlet channel at the same end is filled with an oil phase solution (the solvent is ethylcyclohexane) containing 0.2wt% trimesoyl chloride (filling operation as above), and then standing for 1 minute to generate an interfacial polymerization reaction on the surface of the porous base membrane, and the solution in the water inlet channel is completely blown with compressed air at 40°C, until there is no liquid on the membrane surface, to obtain a roll type composite membrane element;

[0043] S2, to the water flow channel of either end of the roll type composite membrane element, first pass in 40℃ pure water (3 kg pressure) rinse for 10 minutes, then pass in room temperature 500 mg / L sodium hypochlorite aqueous solution (3 kg pressure) rinse for 2 minutes, and finally pass in room temperature 1 wt% sodium bisulfite aqueous solution (3 kg pressure) rinse for 2 minutes, finally get the finished product of high desalination, high desalination seawater desalination reverse osmosis membrane element.

[0044] Comparative Example 1

[0045] The membrane element preparation process of the present case is the same as that of Example 1, except that the rinsing of S2 is not performed, i.e. the present case obtains a roll type composite membrane element without rinsing.

[0046] Comparative Example 2

[0047] The membrane element preparation process of the present case is as follows:

[0048] In the pilot line, a polysulfone porous base membrane with a thickness of 150 microns (surface pore size of 10 nm) is used to prepare a reverse osmosis composite membrane at a speed of 10 meters / minute: the base membrane is immersed in an aqueous solution containing 3wt% m-phenylenediamine, and is left for 30s, and a 25℃ compressed air knife is used to blow the surface of the base membrane to remove droplets, and immediately a slit coating head is used to coat the surface of the base membrane with an oil phase solution containing 0.2wt% trimesoyl chloride (the solvent is ethylcyclohexane), and after 1 minute of interfacial polymerization, the surface of the oil phase solution is completely removed in a 40℃ oven, and then the unwashed reverse osmosis membrane sheet is obtained.

[0049] Comparative Example 3

[0050] On the basis of Comparative Example 2, the unwashed reverse osmosis membrane sheet obtained is used to form a roll type element (the element structure size is the same as that of the base membrane rolling process of Example 1), and to the water flow channel of either end of the roll type element, 40℃ pure water (3 kg pressure) is passed in for 10 minutes, room temperature 500 mg / L sodium hypochlorite aqueous solution (3 kg pressure) is passed in for 2 minutes, and room temperature 1 wt% sodium bisulfite aqueous solution (3 kg pressure) is passed in for 2 minutes, and finally the finished product of reverse osmosis membrane element is obtained.

[0051] Comparative Example 4

[0052] The membrane element preparation process of the present case is as follows:

[0053] A reverse osmosis composite membrane was prepared on a pilot line using a polysulfone porous base membrane (surface pore size 10 nm) having a thickness of 150 microns at a running speed of 10 m / min: the base membrane was immersed in an aqueous solution containing 3 wt% m-phenylenediamine, left to stand for 30 s, and the surface of the base membrane was blown to remove droplets using a 25°C compressed air knife, immediately after which the surface of the base membrane was coated with an oil phase solution containing 0.2 wt% trimesoyl chloride (with ethylcyclohexane as the solvent) using a slit coating head, and interfacial polymerization was carried out for 1 min, after which the surface of the oil phase solution was completely removed in a 40°C oven to obtain a non-rinsed reverse osmosis membrane sheet;

[0054] The non-rinsed reverse osmosis membrane sheet obtained in the foregoing was then successively rinsed in a 40°C pure water tank for 10 min, a room temperature 500 mg / L sodium hypochlorite aqueous solution tank for 2 min, and a room temperature 1 wt% sodium bisulfite aqueous solution tank for 2 min, and finally wound up to obtain a rinsed reverse osmosis membrane sheet.

[0055] Comparative Example 5

[0056] On the basis of Comparative Example 4, the rinsed reverse osmosis membrane sheet obtained was wound to form a spiral element (the element structure size was the same as that in the base membrane winding process of Example 1).

[0057] Test Example

[0058] Performance evaluation of seawater desalination reverse osmosis membranes:

[0059] Membrane sheet performance evaluation: the membrane sheet samples prepared in Comparative Examples 2 and 3 were tested under the following conditions: 32000 mg / L sodium chloride solution as the feed liquid, containing 5 ppm boric acid at the same time, solution temperature 25°C, pH 7.5, and test pressure 5.5 MPa. The flux, desalination rate and boron removal rate of the membrane sheet were tested after 1 hour of operation.

[0060] Performance evaluation: the membrane element samples prepared in the above examples and comparative examples were tested under the following conditions: 32000 mg / L sodium chloride solution as the feed liquid, containing 5 ppm boric acid at the same time, solution temperature 25°C, pH 7.5, test pressure 5.5 MPa, and recovery rate 8%. The flux, desalination rate and boron removal rate of the element were tested after 1 hour of operation.

[0061] The test results are shown in Table 1. In order to facilitate the comparison of the water flux of the membrane sheet and the membrane element, the water production of the membrane element was converted into the water production per unit membrane area (LMH).

[0062] Table 1 Performance of reverse osmosis membranes prepared in examples and comparative examples

[0063]

[0064] As shown in Table 1, the test results of Example 1 and Comparative Example 1 show that the flux, desalination rate and boron removal rate of the element are slightly increased after the rinsing. The test results of Examples 1-3 show that the desalination rate and boron removal rate of the reverse osmosis membrane element prepared by first rolling the base film into an element, then interfacial polymerization and finally rinsing are higher. The test results of Comparative Example 1 and Comparative Example 2 show that the rolling process in the production line can cause the desalination rate and boron removal rate of the membrane sheet to decrease. The test results of Comparative Example 2 and Comparative Example 3 show that the desalination rate and boron removal rate of the membrane sheet decrease after being rolled into an element, indicating that the rolling process causes damage to the desalination layer. The test results of Comparative Example 4 and Comparative Example 5 show that the desalination rate and boron removal rate of the membrane sheet decrease during the rolling process into an element. In addition, the desalination rate and boron removal rate of Comparative Example 4 and Comparative Example 5 are lower than those of Example 1, indicating that the membrane sheet is greatly damaged in the rinsing process and the element rolling process in the production line.

[0065] The above description is merely preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes to the technical solutions and the inventive concept of the present application within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A method for preparing high-desalination, high-boron-removal seawater desalination reverse osmosis membrane elements, characterized in that, Includes the following steps: S1. A porous base membrane and conventional components are conventionally wound to form a spiral base membrane element. The spiral base membrane element has a water inlet channel at least one end. The water inlet channel at one end is filled with an aqueous solution containing amine monomers. After standing, the water inlet channel is purged with a first compressed gas. Then, the water inlet channel at the same end is filled with an oil phase solution containing acyl chloride monomers. After standing again, an interfacial polymerization reaction is generated on the surface of the porous base membrane. After purging the water inlet channel with a second compressed gas, a spiral composite membrane element is obtained. S2. After rinsing the spiral-wound composite membrane element, a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element is obtained.

2. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to claim 1, characterized in that, The porous base membrane has a single-layer structure or a multi-layer structure; The material of the single-layer structure is selected from one or more of polyethylene, polypropylene, polysulfone, sulfonated polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyamide, and polyvinylidene fluoride; The multilayer structure uses polyester nonwoven fabric as the bottom layer and a support layer on its surface. The material of the support layer is one or more of polyethylene, polypropylene, polysulfone, sulfonated polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyamide, and polyvinylidene fluoride. The surface pore size of the porous base membrane is 5 nanometers to 10 micrometers.

3. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to claim 1, characterized in that, The aqueous solution containing the amine monomer has a concentration of 0.5wt%-10wt%, and the amine monomer is selected from one or more of piperazine, m-phenylenediamine, trimethylamine, polyethyleneimine, triethylenetetramine, tetraethylenepentamine, and 1,3,5-triaminobenzene. The solvent in the aqueous solution is water. The concentration of the oil phase solution containing the acyl chloride monomer is 0.05wt%-1wt%, and the acyl chloride monomer is selected from one or more of pyromellitic trisulfonyl chloride, terephthaloyl chloride, isophthaloyl chloride, isophthalosulfonyl chloride, and 1,3,6-naphthalenetrisulfonyl chloride. The solvent in the oil phase solution is a solvent that can dissolve the acyl chloride monomer but is immiscible with water and has a boiling point below 150°C.

4. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to claim 1, characterized in that, The settling time after filling with aqueous solution is 10 seconds to 30 minutes; the settling time after filling with oil solution is 1 second to 5 minutes.

5. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to claim 1, characterized in that, The first compressed gas and the second compressed gas are each selected from one of air, nitrogen, argon, and helium; the temperature of the first compressed gas is 10-70℃; and the temperature of the second compressed gas is in the range of 30-90℃.

6. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to any one of claims 1-5, characterized in that, The rinsing process involves sequentially introducing pure water, sodium hypochlorite aqueous solution, and sodium bisulfite aqueous solution into either end of the water inlet channel for rinsing.

7. The method for preparing a high-desalination, high-boron-removal seawater desalination reverse osmosis membrane element according to claim 6, characterized in that, The temperature of the pure water introduced is 0-100℃, the introduction time is 5 seconds to 10 minutes, and the introduction pressure is 0-60 kg. The concentration of the sodium hypochlorite aqueous solution is 10-5000 mg / L, the temperature is 10-40℃, the introduction time is 5 seconds to 10 minutes, and the pressure is 0-30 kg. The sodium bisulfite aqueous solution has a concentration of 0.1wt%-10wt%, a temperature of 10-100℃, an introduction time of 5 seconds to 10 minutes, and a pressure of 0-30 kg.

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