CN111422977B - Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate - Google Patents

Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate Download PDF

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CN111422977B
CN111422977B CN202010060683.5A CN202010060683A CN111422977B CN 111422977 B CN111422977 B CN 111422977B CN 202010060683 A CN202010060683 A CN 202010060683A CN 111422977 B CN111422977 B CN 111422977B
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silk
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silk fibroin
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CN111422977A (en
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杨明英
王捷
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C02F3/105—Characterized by the chemical composition
    • C02F3/108—Immobilising gels, polymers or the like
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/04—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres
    • D04H1/08—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres having existing or potential cohesive properties, e.g. natural fibres, prestretched or fibrillated artificial fibres and hardened by felting; Felts or felted products
    • D04H1/09—Silk
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a preparation method for constructing a multilayer duplex water treatment biological membrane by taking silkworm plane silks as substrates. The invention comprises the following steps in sequence: obtaining silkworm plane silk and extracting silk fibroin aqueous solution; with silk fibroin and CaCl2And Na2HPO4Constructing hydroxyapatite/silk fibroin biomineralization solution as a first layer of planar silk treatment solution as a reaction reagent; constructing a silicon dioxide/silk fibroin biomineralization solution as a second layer of planar silk treatment solution by taking silk fibroin, APTES and TEOS as reaction reagents; and (3) sequentially soaking the planar filaments in the first layer of mineralized solution and the second layer of mineralized solution, taking out the planar filaments, draining, drying, and repeating for multiple times to finally obtain the multilayer-structure water treatment biomembrane containing the nanoparticles for different types of sewage treatment. The method has the advantages of simple process, convenient operation, environmental protection and no pollution in the whole process, and the prepared planar yarn can be repeatedly utilized, thereby having wide application prospect in the field of sewage treatment.

Description

Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate
Technical Field
The invention belongs to the field of environmental protection application, and particularly discloses a preparation method for constructing a water treatment biological membrane with a multilevel structure by taking silkworm plane silks as a substrate.
Background
At present, water pollution is serious in China, and heavy metal ions and domestic wastes in industrial production cause certain pollution to water. Meanwhile, the middle and western regions face the dilemma of drought and water shortage all the year round, and the embarrassment that drinking water resources are short and water consumption is limited often occurs in the eastern and western regions with high rainfall. The pollution of water resources can directly cause the decline of the health condition of human bodies and seriously affect the public health safety. The mode of water pollution treatment is various, and the sewage treatment is carried out through the mode of powder sedimentation in industrial field, and the impurity in the water is got rid of to the multi-purpose filtration membrane of domestic field. However, both methods have a narrow sewage treatment range and a high treatment cost, and therefore, the development of a water treatment biofilm having excellent performance and low price is of great significance for sewage treatment.
The silkworm plane silk has a loose and porous structure, and has the characteristics of filtration and adsorption similar to a membrane. In addition, the plane silk of the silkworms is easy to store, is not easy to deteriorate and can be repeatedly used.
The silk fiber forming the plane silk is used as high molecular biological protein and can be modified and complexed with various compound ions, so that the adsorption and water filtration capacity of the plane silk is optimized. Therefore, the silkworm plane silk is combined with the powder particles for industrial wastewater treatment, and a multilayer structure and composite water treatment biomembrane is constructed, so that a new water treatment mode can be developed, and the sewage treatment efficiency is improved.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method for constructing a water treatment biological membrane with a multilevel structure by taking silkworm plane silks as a substrate; the method is characterized in that silkworm plane silk is used as a substrate, and inorganic particles are deposited on the surface of the plane silk layer by layer in a layer-by-layer self-assembly mode, so that a multi-layer nanoparticle deposited composite biological membrane is constructed and used for sewage treatment.
The technical scheme adopted by the invention is as follows:
the method specifically comprises the following steps:
step 1) preparing organic glass flat plates with different sizes, placing the silkworms before spinning on the flat plates, and enabling the silkworms to uniformly spin on the surfaces of the flat plates. When the silkworms are completely spun, the planar silkworms with the thickness of 0.1-1mm can be obtained.
Step 2) constructing a nano-particle/silk fibroin mineralized solution system: sequentially adding CaCl into silk fibroin solution2And Na2HPO4Adjusting the pH value of the solution to 9.5, and continuously reacting for 18-24h to obtain a hydroxyapatite/fibroin (HAp/SF) composite solution serving as a first layer of solution for planar silk treatment;
step 3) constructing silicon dioxide/silk fibroin (SiO)2/SF) mineralizing solution system: adding Aminopropyltriethoxysilane (APTES) into silk fibroin solution, stirring, reacting at 4 deg.C for 10-15min, dripping tetraethyl silicate (TEOS), reacting at 4 deg.C for 20min, transferring to 25 deg.C, standing overnight to obtain silicon dioxide/silk fibroin (SiO)2/SF) composite solution as a second layer solution for planar yarn treatment;
step 4), soaking the planar filaments obtained in the step (1) in HAp/SF mineralization liquid for 15-30min, taking out, draining, airing, and repeating the soaking-airing operation for 3-5 times;
step 5) mixingSoaking the planar wire obtained after the treatment in the step (5) in SiO2And/or soaking in the SF mineralization solution for 15-30min, taking out, draining, drying in the air, and repeating the soaking-drying operation for 3-5 times.
Step 6), after the surface of the planar yarn is processed layer by layer in the steps (4) and (5), obtaining the biological membrane which has a multilayer structure and is used for sewage treatment
The thickness of the plane silk in the step 1) is 0.1-1 mm.
The silkworm for spinning can be Bombyx mori, Antheraea Pernyi, and Castanea anea mollissima
CaCl in the step 2)2The concentration of (A) is 15-20mmol/L, Na2HPO4The concentration of (A) is 10-12 mmol/L.
The volume percentage concentration of aminopropyltriethoxysilane in the step 3) is 0.05% -0.5%, and the volume percentage concentration of tetraethyl silicate is 0.2% -2%.
The silk fibroin solution 2) in the step 2) and the step 3) is obtained by degumming, dissolving and dialyzing, and the mass percentage concentration of the silk fibroin solution is 0.1-2%.
The silk fibroin solution in the step 2) and the step 3) can also be a silkworm silk fibroin or an oak silk fibroin solution, and in addition, a starch and cellulose aqueous solution high molecular solution can also be used as a substitute for the experiment.
The other methods for inducing the generation of hydroxyapatite in the step 2) are also applicable, and in addition, the nanoparticles with rough surfaces, such as calcium carbonate, are also applicable to the preparation of the first layer treatment solution.
The silica in the silica/silk fibroin mineralization solution of step 3) can be replaced by manganese dioxide nanoparticles or organic metal framework (MOF)
The steps 5) to 6) are the gradient layer-by-layer treatment and deposition of two mineralized liquids, and the biomembrane with the multilayer structure is obtained by circulating the steps 5) to 6)
The sewage treatment comprises the sewage treatment of heavy metal ions, dyes and organic phenols.
The sewage treatment mode adopts an adsorption or filtration mode.
The invention has the beneficial effects that:
1) the biological membrane constructed by taking the flat wires as the substrate can be repeatedly used for many times, and the utilization rate is high.
2) The hydroxyapatite layer in the biological membrane increases the sewage treatment area, increases the adsorption sites of the next layer of nano particles, and the silica layer enhances the adsorption and catalytic capacity of impurities in the sewage, so that the final treatment effect is obviously improved.
3) The preparation process of the biological membrane is environment-friendly, pollution-free and low in manufacturing cost, and can meet the requirements of different types of sewage treatment.
Detailed Description
The present invention will be described in further detail with reference to examples, which are illustrative of the present invention and are not to be construed as being limited thereto.
Example 1
1) Preparing a flat plate with the size of 1m x 1m, quantitatively placing silkworms to be spun at the later stage of 5 years on the surface of the flat plate to enable the silkworms to be spun freely, and obtaining planar silks with the thickness of about 0.1 mm.
2) Extracting domestic silkworm fibroin solution, and adjusting its concentration to 1%.
3) Taking 50mL of the silk fibroin solution obtained in the step 2), and respectively adding CaCl2(15mmol/L) and Na2HPO4(10mmol/L), then adjusting the pH value of the solution to 9.5, reacting for 24h at 37 ℃ to obtain the mineralized solution for the first layer of the planar yarn (HAp/SF composite solution).
4) Taking 50mL of the silk fibroin solution obtained in the step 2), adding 50 mu L of APTES, violently stirring for several minutes, placing at 4 ℃ for reaction for 10-15min, dropwise adding 200 mu L of TEOS, reacting at 4 ℃ for 20min, transferring to room temperature, standing overnight to obtain SiO2the/SF composite solution is used as a second layer mineralization solution for processing the planar yarn.
5) Cutting the planar filaments obtained in the step 1) into appropriate sizes, soaking in HAp/SF mineralized liquid for 30min, taking out, draining, airing, and repeating the steps for 3-5 times.
6) Soaking the planar wire obtained after the treatment of the step 5) in SiO2And/or soaking in the SF mineralization liquid for 30min for 3-5 times, taking out, draining water, and drying in the air.
7) After the surface is processed layer by layer in the steps 5) and 6), the planar filament is finally dried naturally, and the SiO2/HAp/SF planar filament with a multilayer structure can be obtained and used as a biological membrane for sewage treatment to effectively adsorb heavy metal ions in water. Taking 50mL of common drinking water, adding a certain mass of lead chloride (PbCl) into the water250-100mg), cadmium chloride (CdCl)250-100mg) and ultrasonically dispersed uniformly to simulate a heavy metal polluted water system. And (3) taking a quantitatively prepared biological membrane (20mg), putting the biological membrane into a simulated sewage system, carrying out oscillation reaction for 24h, taking out the biological membrane, measuring the content of heavy metal elements in the treated aqueous solution by using an inductively coupled plasma mass spectrometry, and calculating the heavy metal adsorption capacity of the biological membrane by using a difference value formula. The adsorption results of the composite biological membrane on lead ions and cadmium ions are shown in tables 1 and 2, the adsorption and removal capacity of the composite biological membrane on lead ions reaches 94.5%, the adsorption capacity on cadmium ions is 87%, the adsorption capacity is far higher than that of untreated planar yarns, and the composite biological membrane has excellent sewage treatment capacity.
TABLE 1 adsorption scavenging table of composite membrane for lead ion in polluted water source
Figure GDA0002522609510000041
TABLE 2 adsorption scavenging rate of composite membrane for cadmium ion in polluted water source
Figure GDA0002522609510000042
Example 2
1) Preparing a flat plate with the size of 1m x 1m, quantitatively placing silkworms to be spun at the later stage of 5 years on the surface of the flat plate to enable the silkworms to be spun freely, and obtaining planar silks with the thickness of about 0.2 mm.
2) Extracting domestic silkworm sericin solution, and adjusting its concentration to 0.5%.
3) Taking 50mL of the sericin solution obtained in the step 2), and respectively adding CaCl2(20mmol/L) and Na2HPO4(12mmol/L), adjusting the pH value of the solution to 9.5, and reacting at 37 ℃ for 24 hours to obtain the first-layer processed ore of the planar wireChemical solution (HAp/SS composite solution).
4) Taking 50mL of the sericin solution obtained in the step 2), adding 50 mu L of APTES, violently stirring for several minutes, placing at 4 ℃ for reaction for 10-15min, dropwise adding 200 mu L of TEOS, reacting at 4 ℃ for 20min, transferring to room temperature, standing overnight to obtain SiO2And the/SS composite solution is used as a second layer mineralization solution for processing the planar filaments.
5) Cutting the planar filaments obtained in the step 1) into appropriate sizes, soaking in HAp/SS mineralized liquid for 20min, taking out, draining, airing, and repeating the steps for 3-5 times.
6) Soaking the planar wire obtained after the treatment of the step 5) in SiO2and/SS mineralization liquid is taken out for 30min, drained and dried, the steps are repeated, and the soaking treatment is carried out for 3-5 times.
7) After the surface is processed layer by layer in the steps 5) and 6), the plane wire is finally dried naturally, and SiO with a multilayer structure can be obtained2the/HAp/SS planar yarn prepared can adsorb organic dye in sewage.
Example 3
1) Preparing a flat plate with the size of 1m x 1m, quantitatively placing silkworms to be spun at the later stage of 5 years on the surface of the flat plate to enable the silkworms to be spun freely, and obtaining planar silks with the thickness of about 0.1 mm.
2) Extracting silk fibroin and sericin solution of Bombyx mori respectively, and adjusting the concentration to 1% and 0.5%.
3) Taking 50mL of the silk fibroin solution obtained in the step 2), and respectively adding CaCl2(20mmol/L) and Na2HPO4(12mmol/L), then adjusting the pH value of the solution to 9.5, reacting for 24h at 37 ℃ to obtain the mineralized solution for the first layer of the planar yarn (HAp/SF composite solution).
4) Taking 50mL of the sericin solution obtained in the step 2), adding 100 mu L of APTES, violently stirring for several minutes, placing at 4 ℃ for reaction for 10-15min, dropwise adding TEOS 500 mu L, reacting at 4 ℃ for 20min, transferring to room temperature, standing overnight to obtain SiO2And the/SS composite solution is used as a second layer mineralization solution for processing the planar filaments.
5) Cutting the planar filaments obtained in the step 1) into appropriate sizes, soaking in HAp/SF mineralized liquid for 20min, taking out, draining, airing, and repeating the steps for 3-5 times.
6) Soaking the planar wire obtained after the treatment of the step 5) in SiO2and/SS mineralization liquid is taken out for 30min, drained and dried, the steps are repeated, and the soaking treatment is carried out for 3-5 times.
7) Sequentially soaking the planar wire obtained in the step 6) in HAp/SF mineralized liquid and SiO2and/SS, repeating the steps for multiple times and then airing.
8) And (3) finally obtaining the planar yarn with a multilayer duplex structure through multiple surface treatments in the steps 5) to 7), wherein the prepared planar yarn can adsorb organic phenol in sewage.

Claims (10)

1. A preparation method for constructing a multilayer duplex water treatment biological membrane by taking silkworm plane silks as substrates is characterized by comprising the following steps:
step 1) uniformly placing silkworms on a glass flat plate for spinning, and obtaining a plane silk on the glass flat plate after the silkworms finish spinning;
step 2) constructing a nano-particle/silk fibroin mineralized solution system: sequentially adding CaCl into silk fibroin solution2And Na2HPO4Adjusting the pH value of the solution to 9.5, and continuously reacting for 18-24h to obtain a hydroxyapatite/fibroin composite solution as a first layer solution for treating planar silk;
step 3) constructing a silicon dioxide/silk fibroin mineralized solution system: adding aminopropyltriethoxysilane into the silk fibroin solution, stirring vigorously, reacting at 4 ℃ for 10-15min, dripping tetraethyl silicate, reacting at 4 ℃ for 20min, transferring to room temperature, standing overnight to obtain a silicon dioxide/silk fibroin composite solution as a second layer solution for planar silk treatment;
step 4), soaking the planar filaments obtained in the step (1) in HAp/SF mineralization liquid for 15-30min, taking out, draining, airing, and repeating the soaking-airing operation for 3-5 times;
step 5) soaking the planar wire obtained after the treatment in the step 5 in SiO2Soaking in the SF mineralization solution for 15-30min, taking out, draining, drying in the air, and repeating the soaking-drying operation for 3-5 times;
and 6) after the surface of the planar yarn is processed layer by layer in the steps (4) and (5), obtaining the biological membrane which has a multilayer structure and is used for sewage treatment.
2. The method for preparing the water treatment biomembrane with the bombyx mori planar silk as the substrate in the claim 1, wherein the thickness of the planar silk in the step 1) is 0.1-1 mm.
3. The method for preparing the water treatment biological membrane with the multi-layer duplex structure by using the plane silks of silkworms as the substrate according to claim 1, wherein CaCl in the step 2) is added2The concentration of (A) is 15-20mmol/L, Na2HPO4The concentration of (A) is 10-12 mmol/L.
4. The method for preparing the water treatment biomembrane with the bombyx mori flat silk as the substrate in the multi-layer duplex structure of claim 1, wherein the aminopropyl triethoxysilane is 0.05-0.5% by volume in the solution in the step 3), and the tetraethyl silicate is 0.2-2% by volume in the solution.
5. The method for preparing the water treatment biomembrane with the bombyx mori planar silk as the substrate and the multilayer duplex structure according to claim 1, wherein the mass percentage concentration of the silk fibroin solution in the steps 2) and 3) is 0.1-2%.
6. The method for preparing the water treatment biomembrane with the bombyx mori planar silk as the substrate and the multilayer duplex structure according to claim 1, wherein the silk fibroin solution in the steps 2) and 3) is replaced by silkworm silk fibroin, tussah silk fibroin sericin or starch, and cellulose water-soluble polymer solution.
7. The method for preparing the water treatment biological membrane with the multi-layer duplex structure by using the silkworm planar silk as the substrate according to claim 1, wherein the hydroxyapatite in the hydroxyapatite/silk fibroin composite solution of the step 2) is replaced by calcium carbonate.
8. The method for preparing the water treatment biomembrane with the bombyx mori planar silk as the substrate and the multilayer duplex structure built by the bombyx mori planar silk as the substrate in the claim 1, wherein the silica in the silica/silk fibroin mineralization solution of the step 3) is replaced by manganese dioxide nanoparticles or organic metal framework.
9. The method for preparing the water treatment biomembrane with the bombyx mori flat silk as the substrate in the multi-layer complex structure of claim 1, wherein the biomembrane with the multi-layer structure is obtained by circulating the steps 5) to 6).
10. The method for preparing the water treatment biomembrane with the bombyx mori flat silk as the substrate and the multilayer duplex structure according to claim 1, wherein the sewage treatment comprises the sewage treatment containing heavy metal ions, dyes and organic phenols.
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CN101474429A (en) * 2009-01-22 2009-07-08 浙江理工大学 Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method
CN101502672A (en) * 2009-03-19 2009-08-12 浙江大学 Method for preparing hydroxyapatite/silk fibroin compound porous stand material
CN109647355A (en) * 2018-12-11 2019-04-19 天津工业大学 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide

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Publication number Priority date Publication date Assignee Title
JP3772207B2 (en) * 2002-06-19 2006-05-10 独立行政法人農業生物資源研究所 Biodegradable biopolymer material, production method thereof, and functional material comprising the polymer material

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Publication number Priority date Publication date Assignee Title
CN101235204A (en) * 2008-02-26 2008-08-06 天津工业大学 Method for preparing nano-phase hydroxyapatite/fimbrin composite material
CN101474429A (en) * 2009-01-22 2009-07-08 浙江理工大学 Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method
CN101502672A (en) * 2009-03-19 2009-08-12 浙江大学 Method for preparing hydroxyapatite/silk fibroin compound porous stand material
CN109647355A (en) * 2018-12-11 2019-04-19 天津工业大学 A kind of preparation method of the efficient adsorbents for lead ion pyrolytic of growth in situ manganese dioxide

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