CN111250054A - Group functionalized hypha filter membrane and preparation method and application thereof - Google Patents
Group functionalized hypha filter membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a group functionalized hypha filter membrane and a preparation method and application thereof. The method specifically comprises the following steps: preparing a directional pollutant removing group mother solution by using inorganic salt and an organic group ligand according to the characteristics and types of pollutants; the preparation and functionalization of the mycelium membrane are realized by utilizing solid-liquid homogeneous grafting reaction; finally, a group functionalized hypha filter membrane product for purifying and intercepting characteristic pollutant wastewater is obtained through washing, acidification and stabilization treatment. The method provides the preparation method of the functionalized hypha filter membrane for concentrating and enriching the pollutants in the heavy metal organic waste liquid, can realize concentration and recovery of the heavy metals in the waste water at low cost, has no secondary pollution, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a preparation method and application of a hypha filter membrane for treating and recycling high-difficulty complex organic heavy metal pollutant wastewater.
Background
With the rapid development of economic society and the rapid growth of population, the global demand for high-quality water is increasing, and the treatment of wastewater by adopting an environment-friendly and efficient method is becoming a research focus. However, industrial and agricultural wastewater, municipal wastewater and various mining wastewater contain heavy metals such as copper, lead, arsenic, chromium and zinc, and the concentration of the heavy metals exceeding a certain limit can cause serious harm to human bodies, animals and plants. For example, arsenic has high toxic and carcinogenic, mutagenic effects, and enters human bodies or other organisms through food chains, ground water, to seriously harm human health and the ecological environment. Chromium is also a heavy metal with high toxicity, and a large amount of chromium-containing wastewater is produced in the industries of electroplating, tanning, mining, steelmaking and the like, is seriously harmful to the life health of human bodies, and is one of 129 key pollutants recognized by the United states EPA. Meanwhile, the high-content antibiotics are also remained in the wastewater, so that the water body air is seriously polluted, and the treatment of high-concentration organic wastewater and bacterial residues which have complex components, high chromaticity, high biological toxicity and difficult degradation is a problem acknowledged at home and abroad. Therefore, the research and development of the technology for treating the complex organic heavy metal chelating wastewater is the key point and the difficulty for treating the heavy metal wastewater.
At present, among water treatment methods, an adsorption method is widely applied to purification treatment of heavy metal organic wastewater due to economy, high efficiency and convenience. The activated carbon has high specific surface area and high micropore structure, and is the most common and widely applied adsorbent in the current sewage treatment technology. Although widely used, the selective adsorption is weak, and the selective adsorption is not strong for certain specific heavy metal pollutants. In addition, inorganic mineral-type adsorbing materials such as clay and zeolite are also available in the market, and although they are also applicable, they have similar disadvantages to activated carbon. With the development of material science, people select a traditional adsorbent with strong adsorbability on heavy metals, and the traditional adsorbent is modified to remarkably enhance the adsorbability of an adsorbing material on the heavy metals, for example, a patent with publication number of CN103143325A discloses a preparation method of a glutamic acid intercalated hydrotalcite heavy metal adsorbent, which can effectively adsorb a plurality of heavy metal pollutants such as Pb ions, Cu ions, Cr ions and the like in water pollution, but has the defects of small adsorption capacity, no selective adsorbability and the like.
Aiming at the problems, the invention develops the group functionalized porous mycelium membrane with the directional adsorption property, has the characteristics of group directional adsorption property, selective recovery and resource utilization, reusability and the like, overcomes the technical difficulties that heavy metal in wastewater is difficult to recycle, an adsorbent is difficult to be utilized for multiple times, secondary pollution is large and the like in the traditional process, and can realize the deep treatment and resource recycling of pollutants in the wastewater.
Disclosure of Invention
The invention provides a group functionalized hypha filter membrane and a preparation method and application thereof, and aims to prepare a modifier by compounding inorganic salt mother liquor and organic group mother liquor for modifying aspergillus niger mycelia to prepare the hypha filter membrane for selectively and efficiently treating heavy metal wastewater.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a group functionalized hypha filter membrane comprises the following steps:
s1 composite group mother liquor configuration
Mixing an inorganic salt mother solution and an organic group mother solution at the temperature of 50-60 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain a composite group mother solution;
the inorganic salt mother liquor is one or more of calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor, and is obtained by mixing and then adjusting the pH value to be less than 3 by using acid;
the organic group mother liquor is obtained by mixing one or more of carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfhydryl mother liquor;
s2 hypha surface homogeneous phase modification treatment
Culturing fungus hypha by using a culture medium, inactivating, washing and crushing the hypha, and dissolving the hypha according to the concentration of 100-200 g/L of the hypha to obtain a hypha suspension;
stirring at the temperature of 50-85 ℃, dropwise adding the composite group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after adding, cooling to room temperature, and washing and filtering to obtain wet hypha membrane sheets with the surfaces being modified;
fixation stabilization post-treatment of S3 film
And (3) spraying the wet hypha membrane obtained in the step (S2) with a dilute acid solution with the pH value of 5-6 or a dilute alkali solution with the pH value of 8-9, acidifying or alkalizing, then spraying the wet hypha membrane with an aqueous solution of chitosan, sodium borohydride or polyacrylamide with the concentration of not higher than 0.1% for stabilization, and drying to obtain the hypha filter membrane.
Preferably, the calcium-based mother liquor is an aqueous solution rich in calcium ions, and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions and is prepared by dissolving ferric ion strong acid salt; the polymer mother liquor is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate in water, and the concentration of the inorganic salt mother liquor is not higher than 200 g/L.
Preferably, the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups; the concentration of the organic group mother liquor is not higher than 50 g/L.
Preferably, when the pollutant wastewater is cation wastewater, the mass ratio of the organic group mother liquor in the composite group mother liquor is not less than 50%; when the pollutant wastewater is fluorine-containing wastewater, the mass ratio of the calcium-based mother liquor in the composite group mother liquor is not less than 60%, and the mass ratio of the polymer mother liquor is not less than 10%; when the pollutant wastewater is wastewater containing arsenic and chromium, the mass ratio of the organic mother liquor in the composite group mother liquor is not less than 5%.
The above treatment is a film surface treatment design based on the combined action of intermolecular van der waals force, ionic bonding, covalent coordinate bonding and reductive deposition involved in the water treatment process, and reduces the content of contaminants in an aqueous solution by forming more stable ligands. Including ionic coordination by calcium groups, covalent coordination by organic groups, reductive deposition and displacement by zero-valent iron.
Preferably, the specific culture method of the fungal hyphae in the hyphae surface homogeneous modification treatment in step S2 is as follows: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing; (2) inoculating fungi into the obtained culture medium in sterile environment, placing into an incubator, horizontally shaking, repeatedly washing the obtained mycelium pellet, inactivating in water bath, and crushing to obtain mycelium suspension.
Preferably, the thickness of the wet mycelium membrane sheet with the surface modified in step S2 is 2-4 mm.
Preferably, when the characteristic pollutant wastewater is anion polluted wastewater, the wet mycelium membrane is subjected to acidification treatment in step S3; when the characteristic pollutant wastewater is heavy metal cation wastewater, the wet mycelium membrane is subjected to alkalization treatment in step S3.
The reason for selecting the above treatment is that the surface of the membrane for treating the cation polluted wastewater is subjected to low potential, and the surface of the membrane for treating the anion polluted wastewater is subjected to cationization, so that the positive and negative phase attraction in the treatment process is facilitated, and the treatment effect is better.
Preferably, when the characteristic pollutant wastewater is hexavalent chromium-containing wastewater, the stabilization treatment in step S3 selects an aqueous solution of sodium borohydride.
The above steps reduce ferrous iron to zero-valent iron, so that the film provides further reduction action on the basis of Van der Waals force combination, covalent coordination and ionic bonding when treating wastewater, hexavalent chromium is reduced to trivalent chromium, and divalent iron ions are generated by replacement, thereby reducing the toxicity of chromium stabilized on the surface of the film.
Preferably, the washing in step S2 is pure water washing, and the washing end point is that the COD content in the aqueous solution is less than 20mg/L and no heavy metal ion can be detected.
The invention also provides a thought of the hypha filter membrane prepared by the method, and the hypha filter membrane is in a porous chain structure.
The invention also provides an application of the hypha filter membrane in treating heavy metal organic complex wastewater.
The technical scheme of the invention has the following beneficial effects:
(1) the method for preparing the hypha filter membrane provided by the invention is simple and convenient to operate, low in cost, good in treatment effect and free of secondary pollution, and the prepared hypha filter membrane product has strong impact resistance and flexibility.
(2) According to the method for preparing the hypha filter membrane, provided by the invention, according to different capturing characteristics of different groups on different heavy metals and anions, an inorganic salt mother liquor and an organic group mother liquor are selected to be compounded into a modifier (the volume ratio of the inorganic salt mother liquor to the organic group mother liquor depends on the types of pollutants), the modifier is used for modifying aspergillus niger mycelia, and the obtained hypha filter membrane is used for treating different types of heavy metal wastewater. The selected organic group mother liquor comprises amino, carboxyl, sulfydryl, hydroxyl and other different groups, and the groups have certain stable coordination performance on heavy metals and adsorb heavy metal ions in wastewater. The selected inorganic salt mother liquor contains metal ions such as iron ions, ferrous ions, calcium ions and the like, wherein the iron ions and the ferrous ions can form stable ferric arsenate and ferrous arsenate with arsenate in the wastewater, and the calcium ions can generate calcium fluoride precipitates with fluoride ions in the wastewater, so that the metal ions can effectively remove pollutants such as arsenate, fluoride and the like in the aqueous solution.
(3) The aspergillus niger hypha provided by the invention is modified, acidified and stabilized, and the formed hypha filter membrane is in a porous chain structure in microscopic form and has high porosity. The hypha filter membrane provided by the invention provides more sites for capturing heavy metal ions, and has van der Waals force, ionic bond and multi-group covalent bond composition, so that one or more heavy metals such as lead ions, cadmium ions, chromium ions, copper ions and the like can be efficiently captured.
Drawings
FIG. 1 is an SEM photograph of a hyphal filter obtained in example 1 of the present invention;
FIG. 2 is a macroscopic view of the hypha filter obtained in this example.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; all reagents used in the examples are commercially available unless otherwise specified.
Example 1
The preparation method of the hypha filter membrane for treating the cationic wastewater provided by the embodiment comprises the following steps:
s1 composite group mother liquor configuration
Mixing the inorganic salt mother liquor and the organic group mother liquor at the temperature of 50 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain a composite group mother liquor; wherein the mass of the inorganic salt mother liquor is less than 50 percent.
The inorganic salt mother liquor is obtained by mixing calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor and then adjusting the pH to be less than 3 by using acid, wherein the concentration of the inorganic salt mother liquor is not higher than 200 g/L; wherein the calcium-based mother liquor is an aqueous solution rich in calcium ions and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions and is prepared by dissolving ferric ion strong acid salt; the polymer mother liquor is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate in water.
The organic group mother liquor is obtained by mixing carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfydryl mother liquor, and the concentration of the organic group mother liquor is not higher than 50 g/L; wherein the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups.
S2 hypha surface homogeneous phase modification treatment
Culturing fungal hyphae by using a culture medium, and specifically comprising the following steps: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing to obtain a liquid culture medium; (2) inoculating fungi into the obtained culture medium in sterile environment, and placing into an incubator for horizontal oscillation to obtain fungus hypha pellets.
Inactivating, washing and crushing mycelium pellets, and dissolving the mycelium pellets according to the concentration of 100g/L of mycelium to obtain a mycelium suspension; wherein, the washing end point is that the COD content in the water solution is lower than 20mg/L and no heavy metal ion can be detected.
Stirring at 50 ℃, dropwise adding the composite group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after the addition, cooling to room temperature, washing and filtering to obtain wet hypha membranes with the surfaces modified uniformly, wherein the membrane thickness is 3 mm.
Fixation stabilization post-treatment of S3 film
And (4) spraying the wet hypha membrane obtained in the step (S2) with a dilute alkali solution with the pH value of 8-9 for alkalization, then spraying the wet hypha membrane with a chitosan aqueous solution with the concentration of not higher than 0.1% for stabilization, and drying to obtain a hypha filter membrane product.
FIG. 1 is an SEM photograph of the hypha filter obtained in this example, and it can be seen that the hypha filter has a porous chain-like structure. FIG. 2 is a macroscopic view of the hypha filter obtained in this example. The hypha filter membrane prepared by the embodiment is used for treating cation wastewater, and the removal rate reaches 92%.
Example 2
The embodiment provides a hypha filter membrane for treating low-price arsenic anion-containing wastewater, which comprises the following steps:
s1 composite group mother liquor configuration
Mixing the inorganic salt mother liquor and the organic group mother liquor at the temperature of 50 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain a composite group mother liquor; wherein the mass of the organic group mother liquor accounts for 5-20%;
the inorganic salt mother liquor is obtained by mixing calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor and then adjusting the pH to be less than 3 by using acid, wherein the concentration of the inorganic salt mother liquor is not higher than 200 g/L; wherein the calcium-based mother liquor is an aqueous solution rich in calcium ions, and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water, and the concentration of the calcium ions is 5 g/L; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions, and is prepared by dissolving ferric ion strong acid salt, and the content of the ferric ions is 10 g/L; the polymer mother liquor is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate in water.
The organic group mother liquor is obtained by mixing carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfydryl mother liquor, and the concentration of the organic group mother liquor is not higher than 50 g/L; wherein the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups.
S2 hypha surface homogeneous phase modification treatment
Culturing fungal hyphae by using a culture medium, and specifically comprising the following steps: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing to obtain a liquid culture medium; (2) inoculating fungi into the obtained culture medium in sterile environment, and placing into an incubator for horizontal oscillation to obtain fungus hypha pellets.
Inactivating, washing and crushing mycelium pellets, and dissolving the mycelium pellets according to the concentration of 100g/L of mycelium to obtain a mycelium suspension; wherein, the washing end point is that the COD content in the water solution is lower than 20mg/L and no heavy metal ion can be detected.
And (3) under the condition of stirring at the temperature of 50 ℃, dropwise adding the compound group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after adding, cooling to room temperature, washing and filtering to obtain wet hypha membranes with the surfaces modified uniformly, wherein the membrane thickness is 2 mm.
Fixation stabilization post-treatment of S3 film
And (3) spraying the wet hypha membrane obtained in the step (S2) with a dilute acid solution with the pH value of 4-6 for acidification treatment, then spraying the wet hypha membrane with a chitosan aqueous solution with the concentration of 0.1% for stabilization treatment, and drying to obtain a hypha filter membrane product for treating arsenic anion wastewater.
Example 3
The embodiment provides a hypha filter membrane for treating low-valence chromium cation-containing wastewater, and the preparation method comprises the following steps:
s1 composite group mother liquor configuration
Mixing the inorganic salt mother liquor and the organic group mother liquor at the temperature of 50 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain a composite group mother liquor; wherein the mass of the organic group mother liquor accounts for 5-20%;
the inorganic salt mother liquor is obtained by mixing calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor and then adjusting the pH to be less than 3 by using acid, wherein the concentration of the inorganic salt mother liquor is not higher than 200 g/L; wherein the calcium-based mother liquor is an aqueous solution rich in calcium ions, and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water, and the concentration of the calcium ions is 5 g/L; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions, and is prepared by dissolving ferric ion strong acid salt, and the content of the ferric ions is 10 g/L; the polymer mother liquor is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate in water.
The organic group mother liquor is obtained by mixing carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfydryl mother liquor, and the concentration of the organic group mother liquor is not higher than 50 g/L; wherein the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups.
S2 hypha surface homogeneous phase modification treatment
Culturing fungal hyphae by using a culture medium, and specifically comprising the following steps: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing; (2) inoculating fungi into the obtained culture medium in sterile environment, and placing into an incubator for horizontal oscillation to obtain fungus hypha pellets.
And (3) inactivating, washing and crushing the mycelium pellets, and dissolving the mycelium pellets according to the concentration of 100g/L to obtain a mycelium suspension, wherein the washing end point is that the COD content in the aqueous solution is lower than 20mg/L and no heavy metal ion can be detected.
And (3) under the condition of stirring at the temperature of 50 ℃, dropwise adding the compound group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after adding, cooling to room temperature, washing and filtering to obtain wet hypha membranes with the surfaces modified uniformly, wherein the membrane thickness is 4 mm.
Fixation stabilization post-treatment of S3 film
And (2) spraying the wet hypha membrane obtained in the step S2 with a dilute alkali solution with the pH value of 8-9 for alkalization, then spraying with 0.1% sodium borohydride, then spraying with 0.1% polyacrylamide aqueous solution for stabilization (specifically, spraying with a sodium borohydride aqueous solution), and drying to obtain the hypha filter membrane product for treating the chromium-containing cation wastewater.
Example 4
The embodiment provides a hypha filter membrane for treating fluoride ion-containing wastewater, and the preparation method comprises the following steps:
s1 composite group mother liquor configuration
Mixing the inorganic salt mother liquor and the organic group mother liquor at the temperature of 50 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain a composite group mother liquor; wherein the mass of the organic group mother liquor accounts for 5-20%;
the inorganic salt mother liquor is obtained by mixing calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor and then adjusting the pH to be less than 3 by using acid, wherein the concentration of the inorganic salt mother liquor is not higher than 200 g/L; wherein the calcium-based mother liquor accounts for not less than 60%, the calcium-based mother liquor is an aqueous solution rich in calcium ions, and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water, and the concentration of the calcium ions is 10 g/L; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions and prepared by dissolving ferric ion strong acid salt, and the concentration of the ferric ions is 5 g/L; the polymer mother liquor accounts for not less than 10 percent, and is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate with the concentration of 5g/L in water.
The organic group mother liquor is obtained by mixing carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfydryl mother liquor, and the concentration of the organic group mother liquor is not higher than 50 g/L; wherein the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups.
S2 hypha surface homogeneous phase modification treatment
Culturing fungal hyphae by using a culture medium, and specifically comprising the following steps: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing; (2) inoculating fungi into the obtained culture medium in sterile environment, and placing into an incubator for horizontal oscillation to obtain fungus hypha pellets.
And (3) inactivating, washing and crushing the mycelium pellets, and dissolving the mycelium pellets according to the concentration of 100g/L to obtain a mycelium suspension, wherein the washing end point is that the COD content in the aqueous solution is lower than 20mg/L and no heavy metal ion can be detected.
And (3) under the condition of stirring at the temperature of 50 ℃, dropwise adding the compound group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after adding, cooling to room temperature, washing and filtering to obtain wet hypha membranes with the surfaces modified uniformly, wherein the membrane thickness is 3 mm.
Fixation stabilization post-treatment of S3 film
And (3) spraying the wet hypha membrane obtained in the step S2 with a dilute acid solution with the pH value of 3-4 for acidification treatment, then spraying with 0.1% sodium borohydride, then spraying with 0.1% polyacrylamide aqueous solution for stabilization treatment, and drying to obtain the hypha filter membrane product for treating the fluoride ion-containing wastewater.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a group functionalized hypha filter membrane is characterized by comprising the following steps:
preparation of S1 composite group mother liquor
Mixing inorganic salt mother liquor and organic group mother liquor at the temperature of 50-60 ℃, adjusting the pH of the solution to be less than or equal to 4.5, and then carrying out condensation reflux to obtain composite group mother liquor;
the inorganic salt mother liquor is one or more of calcium-based mother liquor, ferrous-based mother liquor and polymer mother liquor, and is obtained by mixing and then adjusting the pH value to be less than 3 by using acid;
the organic group mother liquor is obtained by mixing one or more of carboxyl mother liquor, hydroxyl mother liquor, amino mother liquor and sulfydryl mother liquor;
s2 hypha surface homogeneous phase modification treatment
Culturing fungus hypha by using a culture medium, inactivating, washing and crushing the hypha, and dissolving the hypha according to the concentration of 100-200 g/L of the mycelium to obtain a hypha suspension;
stirring at 50-85 ℃, dropwise adding the composite group mother liquor obtained in the step S1 into the hypha suspension, condensing and refluxing for more than 1h after adding, cooling to room temperature, and washing and filtering to obtain wet hypha membrane with the surface modified uniformly;
fixation stabilization post-treatment of S3 film
And (3) spraying the wet hypha membrane obtained in the step S2 with a dilute acid solution with the pH value of 5-6 for acidification or spraying the wet hypha membrane obtained in the step S2 with a dilute alkali solution with the pH value of 8-9 for alkalization, then spraying the wet hypha membrane with an aqueous solution of chitosan, sodium borohydride or polyacrylamide with the concentration of not higher than 0.1% for stabilization, and drying to obtain the hypha filter membrane.
2. The method for preparing the hypha filter membrane according to claim 1, wherein the calcium-based mother liquor is an aqueous solution rich in calcium ions and is prepared by dissolving a calcium ion strong acid salt which is easily soluble in water; the ferrous-based mother liquor is a weakly acidic aqueous solution rich in ferrous ions and is prepared by dissolving ferric ion strong acid salt; the polymer mother liquor is prepared by dissolving polymeric ferric sulfate or polymeric aluminum sulfate in water; the concentration of the inorganic salt mother liquor is not higher than 200 g/L.
3. The method for preparing a hypha filter membrane according to claim 1, wherein the carboxyl mother liquor is an aqueous solution rich in ionic carboxyl organic groups; the hydroxyl mother liquor is an aqueous solution rich in hydroxyl organic groups; the amino mother liquor is an aqueous solution rich in amino organic groups; the sulfhydryl mother liquor is an aqueous solution rich in sulfhydryl organic groups; the concentration of the organic group mother liquor is not higher than 50 g/L.
4. The method for preparing the hypha filter membrane according to claim 1, wherein when the pollutant wastewater is cation wastewater, the mass ratio of the organic group mother liquor in the composite group mother liquor is not less than 50%; when the pollutant wastewater is fluorine-containing wastewater, the mass ratio of the calcium-based mother liquor in the composite group mother liquor is not less than 60%, and the mass ratio of the polymer mother liquor is not less than 10%; when the pollutant wastewater is wastewater containing arsenic and chromium, the mass ratio of the organic mother liquor in the composite group mother liquor is not less than 5%.
5. The method for producing a hypha filter membrane according to claim 1, wherein in the hypha surface homogeneous modification treatment in step S2, a specific culture method of fungal hyphae is as follows: (1) peeling and slicing potatoes, adding water, boiling, filtering to obtain a filtrate, adding glucose, dipotassium hydrogen phosphate and magnesium sulfate, fully dissolving to obtain a culture medium, and sterilizing; (2) inoculating fungi into the obtained culture medium in an aseptic environment, placing into an incubator, horizontally shaking, repeatedly washing, inactivating in water bath, and crushing to obtain a fungal mycelium suspension; the thickness of the wet mycelium membrane sheet with the surface modified in the step S2 is 2-4 mm.
6. The method for producing a hypha filter membrane according to claim 1, wherein when the characteristic pollutant wastewater is anion-polluted wastewater, the wet hypha membrane is acidified in step S3; when the characteristic pollutant wastewater is heavy metal cation wastewater, the wet mycelium membrane is subjected to alkalization treatment in step S3.
7. The method for producing a hypha filter membrane according to claim 1, wherein when the characteristic pollutant wastewater is chromium-containing wastewater, an aqueous sodium borohydride solution is selected for the stabilization treatment in step S3.
8. The method for producing a hypha filter membrane according to claim 1, wherein the washing in step S2 is pure water washing, and the washing end point is that the COD content in the aqueous solution is less than 20mg/L and no heavy metal ion can be detected.
9. A hyphal filter membrane produced by the method according to any one of claims 1 to 8, wherein the hyphal filter membrane has a porous chain-like structure.
10. Use of the hypha filter membrane prepared by the method of any one of claims 1 to 8 or the hypha filter membrane of claim 9 in treatment and recycling of complex heavy metal organic polluted wastewater.
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