CN111266092B - Preparation method of mineralized flat plate silk sewage treatment membrane - Google Patents
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention discloses a preparation method of a mineralized flat plate silk sewage treatment membrane. The big silkworms in the silking stage spin in a plane object to obtain flat silks; fixing the periphery of the flat silk, cleaning, and degumming in deionized water to obtain degummed flat silk; soaking the degummed flat silk in an organic alcohol solution to soften the flat silk; then soaking the flat silk in an alcohol solution and washing the flat silk for a plurality of times to solidify the flat silk to obtain post-treated flat silk; and adding the plate filaments after the post-treatment into a mineralization liquid for biomimetic mineralization and drying to obtain the mineralized plate filament sewage treatment membrane. The method can form nanometer apatite particles with certain size and uniform pore diameter on the surface of the flat plate wire, has excellent performance, is environment-friendly and pollution-free in the preparation process, and can be widely applied.
Description
Technical Field
The invention discloses a preparation method of a sewage treatment membrane in the field of adsorption materials, and particularly relates to a preparation method of a mineralized flat plate wire sewage treatment membrane.
Background
Every year, countless people or animals die from diseases caused by sewage, and how to treat the sewage is a worldwide problem. With the progress of science and technology and the improvement of the living standard of people, the standards of industrial water, environmental water and domestic water are continuously improved. Physical adsorption and chemical adsorption are 2 important treatment methods in sewage treatment, and play a key role. Hydroxyapatite is the main inorganic component constituting natural bones and teeth. Due to the low production cost, good biocompatibility and amphipathy, the preparation has main application in the fields of bone tissue engineering, drug slow release carriers, sewage purification and the like. The nano-hydroxyapatite has large specific surface area, hard texture and strong adsorption capacity, and can effectively adsorb harmful chemical substances, heavy metal ions and the like in a water body, so that the nano material with good adsorption effect can be prepared. However, research on nano hydroxyapatite heavy metal adsorption materials is still beginning, and most of the hydroxyapatite adsorption materials obtained through research have the defects of low surface roughness, low porosity, instability and easy agglomeration in an aqueous solution system, low adsorption rate, small adsorption amount, poor separation effect of various heavy metal ions and the like. In addition, the nano-hydroxyapatite is a particle with a nano-scale porous appearance, and if the treatment method is improper, the nano-hydroxyapatite is also easy to become one of pollutants in the water body. Therefore, the above problems of the nano hydroxyapatite particles in sewage treatment limit the application of the nano hydroxyapatite materials in sewage treatment. So far, no preparation method of the nano hydroxyapatite sewage treatment material with simple process, good adsorption effect and stability exists, and an adsorption material prepared by flat wires is lacked.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art, and provides the preparation method of the mineralized flat plate wire sewage treatment membrane for sewage treatment, which has the advantages of simple process, environmental protection and no pollution.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention discloses a preparation method of a mineralized flat plate wire sewage treatment membrane, which comprises the following specific preparation steps:
the method specifically comprises the following steps: preparing flat wires; soaking the flat plate wires in warm water; treating the surface of the flat silk with urea and organic alcohol; biomimetic mineralization of the processed flat wires;
(1) the big silkworms in the silking stage spin in a plane object to obtain flat silks;
(2) fixing the periphery of the flat plate silk in the step (1), cleaning, and degumming in deionized water with the water temperature of 40-80 ℃ to obtain degummed flat plate silk;
(3) soaking the degummed flat silk in the step (2) in an organic alcohol solution to soften the flat silk; then soaking the flat silk in an alcohol solution and washing the flat silk for a plurality of times to solidify the flat silk to obtain post-treated flat silk;
(4) and (4) adding the flat wire after being processed in the step (3) into a mineralization liquid for biomimetic mineralization, and drying to obtain the mineralized flat wire sewage treatment membrane.
In the step (3), the degummed flat silk is soaked in urea solution with the mass concentration of 1-20%.
In the step (3), the softened product is soaked in an ethanol solution with the mass concentration of 80% or a methanol solution with the mass concentration of 80%.
The biomimetic mineralization treatment in the step (4) is as follows: adding the post-treated plate wire material to CaCl with a final concentration of 2-100mM2Solution or final concentration of 10mM Ca (NO)3)2·4H2Soaking in O solution for 1 h; then the final concentration of Na is 12-60mM by a constant flow pump2HPO4Solution or final concentration of 1.2-6mM (NH)4)2HPO4Slowly dripping the solution into the composite solution at a speed of 1-5mL/min, keeping the constant temperature of the solution system at 40-50 ℃, and adjusting the pH constant to 9-10 by slowly dripping NaOH.
The plane object is a sewage treatment film with smooth outer surface and fiber texture, and the structure of the plane object can be composed of micron-sized fibers and nano-sized particles.
Both the nano-hydroxyapatite and the plate wire material have certain ion and organic matter adsorption capacity, but the two materials are used for heavy metal adsorption or organic pollutant adsorption independently and have the defect of limited adsorption quantity. From the bionic angle, the invention utilizes the condition that the most basic structural unit of natural bone tissue is a fibrous structure formed by orderly assembling nano-scale apatite particles on collagen fibers, regulates and controls the nucleation and growth of nano-scale hydroxyapatite on the surface by using the fiber structure of a flat plate wire as a template framework through a bionic biomineralization method, and prepares the bionic mineralized flat plate wire.
The nucleation and growth of the hydroxyapatite are in-situ grown on the surface of the flat plate wire, but are not directly mixed to the surface of the flat plate wire, so that the hydroxyapatite and the flat plate wire interface have firm combination and higher stability. Besides physical adsorption, the mineralized flat filaments also have chemical adsorption to heavy metals and organic pollutants, such as action force of ion exchange between calcium ions and heavy metal ions. In sewage treatment, the two adsorption principles play a role together, so that the composite adsorption capacity is stronger than that of pure nano hydroxyapatite and flat plate wire materials.
Therefore, based on the above situation, the invention uses the flat plate wire as the mineralization regulation template, and induces the nano hydroxyapatite particles to assemble on the surface of the flat plate wire under specific conditions to form the sewage adsorption film with excellent characteristics of high specific surface area, no toxicity, good heavy metal ion and organic pollutant adsorption, and the like, thereby being an efficient sewage treatment material.
Through specific implementation experiments, the nanometer apatite particles with certain size and uniform pore diameter can be formed on the surface of the flat plate wire; the mineralized flat plate filament product has excellent structural stability and excellent heavy metal and organic solvent adsorption performance.
Due to the application of the technical scheme, compared with the prior art, the invention has the following outstanding characteristics:
(1) the stability is good; according to the invention, through a bionic treatment means, the flat wire is used as a template for mineralized substance deposition, nano-scale hydroxyapatite particles grow on the surface of the flat wire, and the flat wire can firmly fix an apatite material and has good stability in a water body;
(2) the operation is simple, the production cycle is short: the preparation process is simple and efficient, and no complex and fussy preparation process is needed;
(3) the preparation method is environment-friendly and pollution-free, does not use organic or toxic reagents, does not cause harm to the environment and testers in the preparation process, and has no adverse effect on human health;
(4) have physical adsorption and chemisorption concurrently, can carry out the high efficiency to multiple heavy metal ion and organic pollutant and adsorb, have extensive application prospect in fields such as industrialization sewage treatment, domestic purifier.
Drawings
FIG. 1 is an optical microscope photograph of a flat filament fiber of example 1;
FIG. 2 is a high power scanning electron micrograph of the mineralized flat filaments obtained in example 2;
FIG. 3 is a high power scanning electron micrograph of the mineralized flat filaments obtained in example 3;
FIG. 4 is a Raman imaging and Raman spectroscopy image of the mineralized flat plate filament obtained in example 3;
fig. 5 is an XRD pattern of the mineralized flat filaments obtained in example 4.
Detailed Description
The present invention is further illustrated by the following examples, which are illustrative of the present invention and are not to be construed as being limited thereto.
The examples of the invention are as follows:
example 1
The embodiment sequentially comprises the following steps:
(1) the big silkworms in the spinning stage spin in a plane object to obtain flat silks with a micro-scale fiber structure (as shown in figure 1);
(2) fixing the periphery of the flat silk in the step (1), cleaning, keeping in deionized water with the water temperature of 40 ℃ for 30min, and degumming;
(3) soaking the degummed flat wire in the step (2) in a 2% urea solution for 30min to soften the crystal structure in the flat wire; soaking the silk in 80% ethanol solution and washing for several times to solidify fibroin in the flat silk to obtain post-treated flat silk;
(4) adding the plate silk material after being processed in the step (3) into a mineralization liquid for biomimetic mineralization. The biomimetic mineralization steps are as follows: adding CaCl2Adding the mixture (with the final concentration of 100mM) into the plate silk material after the post-treatment, and soaking for 1 h; 60mM Na is mixed by a constant flow pump2HPO4Slowly dripping into the composite solution at a speed of 5mL/min, wherein the solution system is kept at a constant temperature of 50 ℃ and the pH is constant at 10 (adjusted by slowly dripping NaOH); and (3) taking out the flat plate filaments after mineralization is carried out for 20 hours, washing soluble salt on the surfaces of the mineralized flat plate filaments, and drying to obtain the mineralized flat plate filament sewage treatment membrane.
Example 2
The embodiment sequentially comprises the following steps:
(1) the big silkworms in the silking stage spin in a plane object to obtain flat silks;
(2) fixing the periphery of the flat silk in the step (1), cleaning, keeping in deionized water with the water temperature of 60 ℃ for 20min, and degumming;
(3) soaking the degummed flat silk in the step (2) with 1% urea solution and washing for several times to solidify fibroin in the flat silk and obtain post-treated flat silk;
(4) adding the plate silk material after being processed in the step (3) into a mineralization liquid for biomimetic mineralization. The biomimetic mineralization steps are as follows: ca (NO)3)2·4H2Adding O (the final concentration is 10mM) into the plate silk material after the post-treatment, and soaking for 1 h; a final concentration of 6mM (NH) was set by a constant flow pump4)2HPO4Slowly dripping into the composite solution at a speed of 2mL/min, wherein the solution system is kept at a constant temperature of 40 ℃ and the pH is constant at 10 (adjusted by slowly dripping NaOH); and (3) taking out the flat plate filaments after mineralization is carried out for 10 hours, washing soluble salt on the surfaces of the mineralized flat plate filaments, and drying to obtain the mineralized flat plate filament sewage treatment membrane.
(5) Scanning electron microscope observation is carried out on the mineralized flat silk sewage treatment membrane obtained in the step (4), and only a few particles appear on the surface of the flat silk fiber (as shown in figure 2), which indicates that the mineralized flat silk is weak in mineralization under the condition (1% urea solution).
Example 3
The embodiment sequentially comprises the following steps:
(1) the big silkworms in the silking stage spin in a plane object to obtain flat silks;
(2) fixing the periphery of the flat silk in the step (1), cleaning, keeping in deionized water with the water temperature of 80 ℃ for 20min, and degumming;
(3) soaking the degummed flat wire in the step (2) in a 10% urea solution for 20min to soften the crystal structure in the flat wire; soaking the silk in 80% methanol solution and washing the silk for several times to solidify fibroin in the flat silk to obtain post-treated flat silk;
(4) will be provided withAnd (4) adding the plate silk material after post-treatment in the step (3) into a mineralization liquid for biomimetic mineralization. The biomimetic mineralization steps are as follows: adding CaCl2 (with the final concentration of 20mM) into the plate wire material after the post-treatment, and soaking for 1 h; 12mM Na was added by a constant flow pump2HPO4Slowly dripping into the composite solution at a speed of 5mL/min, wherein the solution system is kept at a constant temperature of 50 ℃ and the pH is constant at 9 (adjusted by slowly dripping NaOH); and taking out the flat plate filaments after mineralization is carried out for 3 hours, washing soluble salt on the surfaces of the mineralized flat plate filaments, and freeze-drying to obtain the mineralized flat plate filament sewage treatment membrane.
(5) And (4) carrying out scanning electron microscope observation on the mineralized flat silk sewage treatment membrane obtained in the step (4): the surface of the flat filament fibers was found to be covered with a layer of mineralized matter consisting of many nano-sized particles (as shown in fig. 3). Performing Raman spectrum scanning on the mineralized flat wires: the surface of the flat silk fiber is found to have strong hydroxyapatite characteristic peaks, and the distribution of the Raman peak values and the Raman intensity is consistent with the structure of the fiber morphology (as shown in FIG. 4), which indicates that the flat silk under the condition has strong mineralization capability, and the hydroxyapatite can be distributed on the surface of the flat silk fiber.
Example 4
The embodiment sequentially comprises the following steps:
(1) the big silkworms in the silking stage spin in a plane object to obtain flat silks;
(2) fixing the periphery of the flat silk in the step (1), cleaning, keeping in deionized water with the water temperature of 40 ℃ for 50min, and degumming;
(3) soaking the degummed flat wire in the step (2) in a 20% urea solution for 20min to soften the crystal structure in the flat wire; soaking the silk in 80% ethanol solution and washing for several times to solidify fibroin in the flat silk to obtain post-treated flat silk;
(4) adding the plate silk material after being processed in the step (3) into a mineralization liquid for biomimetic mineralization. The biomimetic mineralization steps are as follows: adding CaCl2 (final concentration is 2mM) into the plate wire material after the post-treatment, and soaking for 1 h; 1.2mM of (NH) is pumped through a constant flow pump4)2HPO4At 1mL/minSlowly dropping into the composite solution, wherein the solution system is kept at a constant temperature of 80 ℃ and the pH is constant at 10 (adjusted by slowly dropping NaOH); taking out the flat plate silk after 4h of mineralization, washing to clean the dissolubility of the surface of the mineralized flat plate silk, putting the mineralized flat plate silk into a muffle furnace, and calcining for 2h at 350 ℃ to obtain the mineralized flat plate silk sewage treatment membrane, wherein XRD analysis shows that the inorganic substance is a hydroxyapatite component (as shown in figure 5).
(5) And (3) adding the mineralized flat silk sewage treatment membrane obtained in the step (4) into sewage containing rhodamine B dye (organic matter), stirring for 2 hours at the temperature of 25-30 ℃, and gradually lightening the bluish red color in the solution, thereby proving that the mineralized flat silk has an obvious effect of absorbing organic pollutants.
Therefore, the method can form nano apatite particles with a certain size and uniform pore diameter on the surface of the flat wire, has excellent performance, is environment-friendly and pollution-free in the preparation process, and can be widely applied.
Finally, it should also be noted that the above list is only a specific implementation example of the present invention. It is obvious that the invention is not limited to the above embodiment examples, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (3)
1. A preparation method of a mineralized flat silk sewage treatment membrane is characterized by sequentially comprising the following steps:
(1) the big silkworms in the silking stage spin in a plane object to obtain flat silks;
(2) fixing the periphery of the flat plate silk in the step (1), cleaning, and degumming in deionized water with the water temperature of 40-80 ℃ to obtain degummed flat plate silk;
(3) soaking the degummed flat silk in the step (2) in a urea solution to soften the flat silk; then soaking the flat silk in an alcohol solution and washing the flat silk for a plurality of times to solidify the flat silk to obtain post-treated flat silk;
in the step (3), the degummed flat silk is soaked in a urea solution with the mass concentration of 10-20%;
(4) and (4) adding the flat wire after being processed in the step (3) into a mineralization liquid for biomimetic mineralization, and drying to obtain the mineralized flat wire sewage treatment membrane.
2. The method for preparing the mineralized flat plate silk sewage treatment membrane according to claim 1, wherein the method comprises the following steps: in the step (3), the softened product is soaked in an ethanol solution with the mass concentration of 80% or a methanol solution with the mass concentration of 80%.
3. The method for preparing the mineralized flat plate silk sewage treatment membrane according to claim 1, wherein the method comprises the following steps: the biomimetic mineralization treatment in the step (4) is as follows: adding the post-treated plate wire material to CaCl with a final concentration of 2-100mM2Soaking the solution for 1h to obtain a composite solution; then the final concentration of Na is 12-60mM by a constant flow pump2HPO4Solution or final concentration of 1.2-6mM (NH)4)2HPO4Slowly dripping the solution into the composite solution at a speed of 1-5mL/min, keeping the constant temperature of the solution system at 40-50 ℃, and adjusting the pH constant to 9-10 by slowly dripping NaOH.
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Citations (2)
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| CN102532573A (en) * | 2012-02-20 | 2012-07-04 | 浙江大学 | Rapid molding method of sericin/hydroxyapatite composite membrane |
| CN106700566A (en) * | 2016-12-30 | 2017-05-24 | 南通纺织丝绸产业技术研究院 | Soft and transparent silk fibroin membrane and preparation method thereof |
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| CN102526801B (en) * | 2012-02-20 | 2014-07-16 | 浙江大学 | Preparation method for flexible sericin protein/hydroxyapatite composite membrane |
| CN104928908B (en) * | 2015-07-10 | 2017-04-12 | 浙江大学 | Method for mineralizing silk fiber |
| CN105085958B (en) * | 2015-09-17 | 2017-10-03 | 李爱冰 | A kind of fixed film of polyphenol oxidase efficient nano absorption and preparation method based on modified silk albumen |
| CN106757387A (en) * | 2017-01-10 | 2017-05-31 | 南丹县农业局 | The preparation method of golden yellow flat board silk |
| CN109380183A (en) * | 2018-10-26 | 2019-02-26 | 广西大学 | A kind of silkworm flat plate silk spinning device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532573A (en) * | 2012-02-20 | 2012-07-04 | 浙江大学 | Rapid molding method of sericin/hydroxyapatite composite membrane |
| CN106700566A (en) * | 2016-12-30 | 2017-05-24 | 南通纺织丝绸产业技术研究院 | Soft and transparent silk fibroin membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 蚕吐平板丝制作技术研究;彭云武 等;《安徽农业科学》;20071231;第35卷(第4期);第1237页 * |
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