CN107519847B - Preparation method of heavy metal ion adsorption membrane - Google Patents
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- CN107519847B CN107519847B CN201710682614.6A CN201710682614A CN107519847B CN 107519847 B CN107519847 B CN 107519847B CN 201710682614 A CN201710682614 A CN 201710682614A CN 107519847 B CN107519847 B CN 107519847B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a preparation method of a heavy metal ion adsorption membrane, belonging to the field of environmental engineering. The preparation method of the invention adds wool powder with a certain proportion into a high molecular material solution dissolved in an organic solvent, and adopts a directional freezing technology to control the growth direction of ice crystals to form a regular structure. The frozen aqueous phase high molecular material solution is frozen and dried in a vacuum low-temperature environment to form a hollow fiber array structure, so that the filtering efficiency is improved. The organic solvent in the invention is selected from organic solvents with high freezing points, so that the freezing time is greatly shortened, the energy loss is avoided, and the preparation method has simple process and low cost; the ultra-clean water filtering membrane prepared by combining the adsorption performance of the wool powder has uniform pore diameter, and can be widely applied to the fields of chemical industry, petroleum, light industry, daily chemicals and the like.
Description
Technical Field
The invention relates to a preparation method of a heavy metal ion adsorption membrane, belonging to the field of environmental engineering.
Background
With the rapid increase of economy, the development of cities and agricultural industries is extremely rapid, and a large amount of heavy metals are discharged into the environment through various ways, so that serious heavy metal pollution is caused. Heavy metal pollutants have the characteristics of high toxicity, difficult degradation, biological enrichment and the like, and can enter human bodies through food chains, drinking water, respiration or skin contact and other ways to harm human health, wherein the four heavy metals of arsenic, chromium, cadmium and nickel can increase the risk of lung cancer, skin cancer, digestive tract cancer, breast cancer and other cancers of the human bodies; the four heavy metals of lead, cadmium, mercury and arsenic can interfere the metabolism of human hormones, and cause various diseases of the central system, the reproductive system and the cardiovascular system; in addition, copper, manganese, zinc and the like are trace elements necessary for human bodies, but excessive intake of copper, manganese, zinc and the like can cause harm to human health. Therefore, the development of an effective and environment-friendly heavy metal ion adsorption material has important significance for protecting the health of water bodies, the environment and the health of human beings.
At present, the treatment methods of heavy metal ions mainly comprise: chemical, biological, and physicochemical. In the invention patent of application No. 200710056397.6, a heavy metal ion adsorption membrane and a preparation method thereof are described, wherein the heavy metal ion adsorption membrane is composed of polyvinyl alcohol and amino polymer, and a three-dimensional polymer network is formed by cross-linking through a cross-linking agent. The introduction of amino not only enhances the water swelling property of the polyvinyl alcohol membrane, but also greatly improves the adsorption capacity of the membrane to heavy metal ions. But consumes a large amount of amino groups during the crosslinking process, reducing the ability to handle heavy metal ions.
The invention has the following patent: the invention relates to an environment-friendly heavy metal ion adsorption material and a preparation method thereof. However, a large amount of chemical reagents are added in the preparation process, and the process flow is complicated and consumes long time, so that the method is not beneficial to industrial production. In the patent with application number 201610273898.9, the invention introduces a heavy metal ion adsorption membrane and a preparation method thereof, wherein the adsorption membrane is composed of a metal organic framework material, 2-mercaptobenzimidazole, a modifier, a stabilizer and other organic solvents, and can enhance the adsorption capacity of the adsorption membrane on heavy metal ions. However, in the method, a large amount of reagents and organic solvents are used in the preparation process, the adsorption film has secondary damage to the water body caused by the organic solvents and the residues of the reagents, and the preparation process flow is complex and tedious. Therefore, it is very important to prepare an efficient, environment-friendly and cheap adsorbing material. The interior of the porous structure obtained by the preparation method is a disordered porous structure, and the speed of treating heavy metal ions is low and the treatment capacity is small.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing a heavy metal ion adsorption membrane, and to achieve the above object, the technical solution of the present invention:
a preparation method of a heavy metal ion adsorption membrane comprises the following steps:
a. preparation of high molecular material/wool powder solution
Adding a high polymer material into dimethyl sulfoxide or 1, 4-dioxane, stirring until the high polymer material is completely dissolved, adding wool powder into a high polymer material solution, stirring for 1-4 hours, placing the solution in an environment with a vacuum degree of 0.05-0.1 MPa for 2-5 hours, and removing bubbles in the solution to obtain the high polymer material/wool powder solution.
Wherein, the high polymer material is one of polyurethane, polyacrylonitrile or polylactic acid.
The specification of the wool powder is 300-800 meshes.
The mass ratio of the wool powder to the high polymer material is 1: 1-2: 1.
the mass fraction of the high polymer material/wool powder solution is 4-6%.
b. Preparation of high polymer material/wool powder body
Placing a mould above a metal conductor, soaking the metal conductor in liquid nitrogen, pouring the polymer material/wool powder solution prepared in the step a into the mould, forming a solution layer with the height of 5-10 mm in the mould, slowly solidifying the polymer material/wool powder solution in the mould from bottom to top along the vertical direction of the mould under the action of low temperature of the liquid nitrogen to form a columnar unit with an organic solvent crystal as a core and a polymer material/wool powder as a skin, and taking out a blank of a polymer material/wool powder blank with a wall surface between adjacent unit bodies from the mould for later use.
Wherein the die is a through columnar body made of polytetrafluoroethylene material and having a wall thickness of 3-10 mm.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 to minus 65 ℃ and the vacuum degree of 2 to 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank, forming hollow pipes with the aperture of 30 to 100 mu m and the wall thickness of 1 to 5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption membrane after 24 to 36 hours.
The metal conductor is one of a copper conductor, an aluminum conductor or a silver conductor.
Due to the adoption of the technical scheme, the wool powder capable of effectively adsorbing heavy metal ions in water is added in the preparation process, and the wool powder is a protein and has a good adsorption effect on the heavy metal ions; in addition, the adsorption effect of the wool powder is closely related to the particle size, the smaller the particle size is, the larger the filtering area is, and the better the adsorption effect is, so that the specification of the wool powder is 800-900 meshes. The polyurethane, polyacrylonitrile and polylactic acid high molecular material has good chemical stability, and can prolong the service life of the filter material.
The preparation method of the invention adopts the directional freezing technology to induce the growth of the ice crystals, the die is placed on the metal conductor block, the metal conductor is soaked in liquid nitrogen, the upper end of the die is opened, the low temperature of liquid nitrogen is transferred through the metal conductor at the lower end, the high molecular material/wool powder solution in the die is slowly solidified from bottom to top along the vertical direction of the die, the high molecular material/wool powder in the solution is gathered and rearranged under the pushing and pushing repulsion of directionally grown and solidified ice crystals, finally a columnar unit taking organic solvent crystals as a core and water phase high molecular material as a skin is formed, and the core layer in each unit body is directly sublimated and removed by the solidified and molded blank body of the hollow fiber array structure on the common wall surface between the adjacent unit bodies in the low-pressure and low-temperature environment, the heavy metal ion adsorption membrane is of an array structure with hollow fibers with the aperture of 30-100 mu m and the wall thickness of 1-5 mu m and the common wall surfaces between adjacent hollow fibers.
In order to avoid the influence of the external environment temperature on the freezing of the solution and further ensure the final integrity of the material, the material of the die is made of polytetrafluoroethylene material with poor heat conductivity and has certain wall thickness. In addition, in order to freeze the solution in a short time and reduce the excessive waste of energy, the through column body is selected by the die, so that the direct contact between the metal conductor and the solution is facilitated; the metal conductor selects copper, aluminum or silver with better heat conductivity coefficient; the organic solvent is selected from one of dimethyl sulfoxide or 1, 4-dioxane with high freezing point. The solution layer height that solution formed in the mould is 5 ~ 10mm, finally forms the heavy metal ion adsorption membrane that 5 ~ 10mm is thick, the heavy metal ion adsorption membrane mechanical properties who forms when freezing in-process solution layer height is lower is relatively poor, when solution layer height is higher, be unfavorable for solution to freeze fast, waste a large amount of energy, and when solution layer thickness, final heavy metal ion adsorption membrane thickness is thicker, greatly reduced its filter effect, consequently the height of solution is finally between 5 ~ 10mm in the mould.
A large amount of bubbles can be generated in the solution dissolving process due to stirring, and the array structure is destroyed in the freezing process by the bubbles, so that the bubbles need to be removed before the solution is directionally frozen, and the method is mainly realized by a vacuum defoaming method. And (3) placing the stirred solution in an environment with the vacuum degree of 0.05-0.1 MPa for defoaming, and standing for 2-5 hours in a low-pressure environment according to the mass fraction of the high-molecular material/wool powder body in the solution so as to fully remove bubbles in the solution.
In the forming process of the blank, the hollow array structure is clearer along with the increase of the mass fraction of the high molecular material/wool powder blank in the solution, but the aperture is gradually reduced, and the wall thickness is increased, so the aperture size can be regulated and controlled by the simple method, and the use requirements of different places are met. However, as the mass fraction of the polymer material/wool powder body in the solution increases, the viscosity of the solution gradually rises, the viscosity is too high, the organic solvent crystals which are directionally grown and solidified in the freezing process do not have enough force to push and repel the polymer material in the solution, so that the polymer material is aggregated and rearranged, finally, the formed pores gradually tend to be in a closed state, and the pores which tend to be closed can influence the filtering effect in use. Therefore, the mass fraction of the high polymer material/wool powder body is controlled to be 4-6%. Wherein the mass ratio of the wool powder to the high polymer material is 1: 1-2: 1, when the wool powder content is less, the adsorption effect is not obvious enough, but when the wool powder content is higher, a large amount of wool powder blocks the gap to enable the liquid to pass through, and the filtering effect is reduced.
The preparation method adopts the directional freezing technology to induce the ice crystal growth and the freeze drying technology, has simple process and low cost, and can not cause the waste of resources and the environmental pollution.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
along with the rapid increase of economy, the development of cities and agricultural industries is extremely rapid, a large amount of heavy metals are discharged into the environment through various ways, serious heavy metal pollution is caused, and wool is used as natural protein and has good adsorption performance on heavy metal ions. The directional freezing technology induces the growth of ice crystals, and removes solvent components under the low-temperature and low-pressure environment to form a high-orientation hollow fiber array structure, so that the high polymer material has a larger specific surface area, and therefore, the high polymer material has better adsorbability and water absorbability.
A preparation method of a heavy metal ion adsorption membrane comprises the following steps:
a. preparation of high molecular material/wool powder solution
Adding one of three polymer materials of polyurethane, polyacrylonitrile or polylactic acid into dimethyl sulfoxide or 1, 4-dioxane, and stirring until the polymer materials are completely dissolved, wherein the mass ratio of wool components to the polymer materials is 1: 1-2: 1 adding 300-800-mesh wool powder into the solution, stirring for 1-4 hours, placing in an environment with a vacuum degree of 0.05-0.1 MPa for 2-5 hours, and removing bubbles in the solution to obtain a high polymer material/wool powder solution with a mass fraction of 4-6%.
b. Preparation of high polymer material/wool powder body
Placing a through columnar body mold made of polytetrafluoroethylene material and having a wall thickness of 3-10 mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 5-10 mm in the mold, and under the action of the liquid nitrogen at low temperature, slowly solidifying the polymer material/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form a columnar body unit taking organic solvent crystals as a core and polymer material/wool powder as a skin, taking out a blank of a polymer material/wool powder blank body on the common wall surface between adjacent unit bodies, and taking out the blank from the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 to minus 65 ℃ and the vacuum degree of 2 to 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank, forming hollow pipes with the aperture of 30 to 100 mu m and the wall thickness of 1 to 5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption membrane after 24 to 36 hours.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example one
a. Preparation of polyurethane/wool powder solution
Adding 2g of polyurethane into 96g of dimethyl sulfoxide, stirring until the polyurethane is completely dissolved, adding 2g of 300-mesh wool powder into the solution, stirring for 1h, placing the solution in an environment with the vacuum degree of 0.05MPa for 2h, and removing bubbles in the solution to obtain a polyurethane/wool powder solution with the mass fraction of 4%.
b. Preparation of polyurethane/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 3mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold, forming a solution layer with a height of 5mm in the mold, and under the action of the liquid nitrogen at low temperature, slowly solidifying the polyurethane/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form a cylindrical unit taking dimethyl sulfoxide crystals as a core and polyurethane and wool powder as skins, and taking out a blank of a polyurethane/wool powder blank with a wall surface between adjacent unit bodies, wherein the blank is taken out of the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 ℃ and the vacuum degree of 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 70-100 mu m and the wall thickness of 1-2 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 36 hours.
Example two
a. Preparation of polyurethane/wool powder solution
Adding 2g of polyurethane into 95g of 1, 4-dioxane, stirring until the polyurethane is completely dissolved, adding 3g of 500-mesh wool powder into the solution, stirring for 2.5h, placing the solution in an environment with the vacuum degree of 0.07MPa for 3h, and removing bubbles in the solution to obtain the polyurethane/wool powder solution with the mass fraction of 5%.
b. Preparation of polyurethane/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 7mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 7mm in the mold, and under the action of low temperature of the liquid nitrogen, slowly solidifying the polyurethane/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form a cylindrical unit with 1, 4-dioxane crystal as a core, polyurethane and wool powder as skins, and taking out a blank of a polyurethane/wool powder blank with a common wall surface between adjacent unit bodies from the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 60 ℃ and the vacuum degree of 3Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 50-70 mu m and the wall thickness of 2-3 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 30 hours.
EXAMPLE III
a. Preparation of polyurethane/wool powder solution
Adding 2g of polyurethane into 94g of dimethyl sulfoxide, stirring until the polyurethane is completely dissolved, adding 4g of 800-mesh wool powder into the solution, stirring for 4 hours, placing the solution in an environment with a vacuum degree of 0.1MPa for 5 hours, and removing bubbles in the solution to obtain a polyurethane/wool powder solution with a mass fraction of 6%.
b. Preparation of polyurethane/wool powder body
Placing a through cylindrical body mould made of polytetrafluoroethylene material and having the wall thickness of 10mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mould to form a solution layer with the height of 10mm in the mould, slowly solidifying the polyurethane/wool powder solution in the mould from bottom to top along the vertical direction of the mould under the action of the low temperature of the liquid nitrogen to form a cylindrical body unit taking dimethyl sulfoxide crystals as a core and polyurethane and wool powder as skins, taking out a blank body of a polyurethane/wool powder blank body on the common wall surface between adjacent unit bodies, and taking the blank body out of the mould for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 65 ℃ and the vacuum degree of 2Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 30-50 mu m and the wall thickness of 3-5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 24 hours.
Example four
a. Preparation of polyacrylonitrile/wool powder solution
Adding 2g of polyacrylonitrile into 96g of 1, 4-dioxane, stirring until the polyacrylonitrile is completely dissolved, adding 2g of 300-mesh wool powder into the solution, stirring for 1h, placing the solution in an environment with the vacuum degree of 0.05MPa for 2h, and removing bubbles in the solution to obtain the polyacrylonitrile/wool powder solution with the mass fraction of 4%.
b. Preparation of polyacrylonitrile/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 3mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 5mm in the mold, and under the action of the liquid nitrogen at low temperature, slowly solidifying the polyacrylonitrile/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form cylindrical units with 1, 4-dioxane crystals as cores and polyacrylonitrile and wool powder as skins, and taking out blanks of polyacrylonitrile/wool powder blanks on the common wall surface between adjacent unit bodies from the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 ℃ and the vacuum degree of 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 70-100 mu m and the wall thickness of 1-2 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 36 hours.
EXAMPLE five
a. Preparation of polyacrylonitrile/wool powder solution
Adding 2g of polyacrylonitrile into 95g of dimethyl sulfoxide, stirring until the polyacrylonitrile is completely dissolved, adding 3g of 500-mesh wool powder into the solution, stirring for 2.5h, placing the solution in an environment with the vacuum degree of 0.07MPa for 3h, and removing bubbles in the solution to obtain a polyacrylonitrile/wool powder solution with the mass fraction of 5%.
b. Preparation of polyacrylonitrile/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 7mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 7mm in the mold, slowly solidifying the polyacrylonitrile/wool powder solution in the mold from bottom to top along the vertical direction of the mold under the action of the low temperature of the liquid nitrogen to form cylindrical units taking dimethyl sulfoxide crystals as cores and polyacrylonitrile and wool powder as skins, taking blanks of polyacrylonitrile/wool powder blanks on the common wall surface between adjacent unit bodies out of the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 60 ℃ and the vacuum degree of 3Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 50-70 mu m and the wall thickness of 2-3 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 30 hours.
EXAMPLE six
a. Preparation of polyacrylonitrile/wool powder solution
Adding 2g of polyacrylonitrile into 94g of 1, 4-dioxane, stirring until the polyacrylonitrile is completely dissolved, adding 4g of 800-mesh wool powder into the solution, stirring for 4h, placing the solution in an environment with the vacuum degree of 0.1MPa for 5h, and removing bubbles in the solution to obtain the polyacrylonitrile/wool powder solution with the mass fraction of 6%.
b. Preparation of polyacrylonitrile/wool powder body
Placing a through columnar body mold made of polytetrafluoroethylene material and having the wall thickness of 10mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold, forming a solution layer with the height of 10mm in the mold, and under the action of the liquid nitrogen at low temperature, slowly solidifying the polyacrylonitrile/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form columnar body units taking 1, 4-dioxane crystals as cores and polyacrylonitrile and wool powder as skins, and taking out blanks of polyacrylonitrile/wool powder blanks on the common wall surface between adjacent unit bodies from the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 65 ℃ and the vacuum degree of 2Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 30-50 mu m and the wall thickness of 3-5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 24 hours.
EXAMPLE seven
a. Preparation of polylactic acid/wool powder solution
Adding 2g of polylactic acid into 96g of dimethyl sulfoxide, stirring until the polylactic acid is completely dissolved, adding 2g of 300-mesh wool powder into the solution, stirring for 1h, placing the solution in an environment with the vacuum degree of 0.05MPa for 2h, and removing bubbles in the solution to obtain the polylactic acid/wool powder solution with the mass fraction of 4%.
b. Preparation of polylactic acid/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 3mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 5mm in the mold, slowly solidifying the polylactic acid/wool powder solution in the mold from bottom to top along the vertical direction of the mold under the action of the low temperature of the liquid nitrogen to form a cylindrical unit taking dimethyl sulfoxide crystals as a core and polylactic acid and wool powder as skins, taking out a blank of a polylactic acid/wool powder blank with a wall surface between adjacent unit bodies, and taking the blank out of the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 ℃ and the vacuum degree of 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 70-100 mu m and the wall thickness of 1-2 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 36 hours.
Example eight
a. Preparation of polylactic acid/wool powder solution
Adding 2g of polylactic acid into 95g of 1, 4-dioxane, stirring until the polylactic acid is completely dissolved, adding 3g of 500-mesh wool powder into the solution, stirring for 2.5h, placing the solution in an environment with the vacuum degree of 0.07MPa for 3h, and removing bubbles in the solution to obtain the polylactic acid/wool powder solution with the mass fraction of 5%.
b. Preparation of polylactic acid/wool powder body
Placing a through cylindrical mold made of polytetrafluoroethylene material and having a wall thickness of 7mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold to form a solution layer with a height of 7mm in the mold, and under the action of low temperature of the liquid nitrogen, slowly solidifying the polylactic acid/wool powder solution in the mold from bottom to top along the vertical direction of the mold to form a cylindrical unit with 1, 4-dioxane crystal as a core, polylactic acid and wool powder as skins, and taking out the blank of the polylactic acid/wool powder blank on the common wall surface between adjacent unit bodies from the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 60 ℃ and the vacuum degree of 3Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 50-70 mu m and the wall thickness of 2-3 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 30 hours.
Example nine
a. Preparation of polylactic acid/wool powder solution
Adding 2g of polylactic acid into 94g of dimethyl sulfoxide, stirring until the polylactic acid is completely dissolved, adding 4g of 800-mesh wool powder into the solution, stirring for 4h, placing the solution in an environment with a vacuum degree of 0.1MPa for 5h, and removing bubbles in the solution to obtain a polylactic acid/wool powder solution with a mass fraction of 6%.
b. Preparation of polylactic acid/wool powder body
Placing a through columnar body mold made of polytetrafluoroethylene material and having the wall thickness of 10mm above a metal conductor made of copper or aluminum or silver, soaking the metal conductor in liquid nitrogen, pouring the high polymer material/wool powder solution prepared in the step a into the mold, forming a solution layer with the height of 10mm in the mold, and slowly solidifying the polylactic acid/wool powder solution in the mold from bottom to top along the vertical direction of the mold under the action of the low temperature of the liquid nitrogen to form columnar body units taking dimethyl sulfoxide crystals as cores and polylactic acid and wool powder as skins, wherein the polylactic acid/wool powder bodies on the common wall surface between the adjacent unit bodies are blank bodies, and the blank bodies are taken out of the mold for later use.
c. Preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 65 ℃ and the vacuum degree of 2Pa for freeze drying, removing the core in the cylindrical body unit in the blank to form hollow pipes with the aperture of 30-50 mu m and the wall thickness of 3-5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption film after 24 hours.
Claims (2)
1. The preparation method of the heavy metal ion adsorption membrane is characterized by comprising the following steps:
a. preparation of high molecular material/wool powder solution
Adding a high polymer material into dimethyl sulfoxide or 1, 4-dioxane, stirring until the high polymer material is completely dissolved, adding wool powder into a high polymer material solution, stirring for 1-4 hours, placing the solution in an environment with a vacuum degree of 0.05-0.1 MPa for 2-5 hours, and removing bubbles in the solution to obtain a high polymer material/wool powder solution;
wherein the high polymer material is one of polyurethane or polyacrylonitrile;
the specification of the wool powder is 300-800 meshes;
the mass ratio of the wool powder to the high polymer material is 1: 1-2: 1;
the mass fraction of the high polymer material/wool powder solution is 4-6%;
b. preparation of high polymer material/wool powder body
Placing a mould above a metal conductor, soaking the metal conductor in liquid nitrogen, pouring the polymer material/wool powder solution prepared in the step a into the mould, forming a solution layer with the height of 5-10 mm in the mould, slowly solidifying the polymer material/wool powder solution in the mould from bottom to top along the vertical direction of the mould under the action of low temperature of the liquid nitrogen to form a columnar unit with an organic solvent crystal as a core, polymer material/wool powder as a skin, taking out a blank of a polymer material/wool powder blank with a wall surface between adjacent unit bodies, and taking out the blank from the mould for later use;
wherein the die is a through columnar body made of polytetrafluoroethylene material and having a wall thickness of 3-10 mm;
c. preparation of heavy metal ion adsorption film
And c, placing the blank prepared in the step b in an environment with the temperature of minus 55 to minus 65 ℃ and the vacuum degree of 2 to 5Pa for freeze drying, removing the core in the cylindrical body unit in the blank, forming hollow pipes with the aperture of 30 to 100 mu m and the wall thickness of 1 to 5 mu m, forming an array structure with the wall surfaces shared by the adjacent hollow pipes, and obtaining the heavy metal ion adsorption membrane after 24 to 36 hours.
2. The method for preparing a heavy metal ion adsorption membrane according to claim 1, wherein: the metal conductor is one of a copper conductor, an aluminum conductor or a silver conductor.
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