Preparation method and application of alginate-protein interpenetrating network fiber
By preparing alginic acid-protein to penetrate network fiber and use sludge resources for soil repair, the problem of environmental pollution of sludge resources and the environmental pollution of traditional restoration agents can be solved, and efficient and environmentally friendly soil repair effects are achieved.
Patent Information
- Application Number
- CN202411452055.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-17
- Publication Date
- 2025-01-21
AI Technical Summary
The prior art is difficult to effectively utilize sludge resources, and traditional remediation agents have problems in reducing the heavy metal content in soil.
By mixed raw materials by mixed sludge protein, sodium alginate and sludge-based alginate, and to form a network structure, the alginate-protein-protein-protein interoperability was used as soil to be used as soil. Repair medium use.
The efficient utilization of sludge resources has been realized, the dependence on traditional raw materials has been reduced, it has good mechanical performance and degradation performance, reduces environmental pollution, and can effectively improve the soil environment.
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Figure CN119332370A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of sludge treatment, and in particular relates to a preparation method and application of alginate-protein interpenetrating network fibers. Background Art
[0002] The main pollution is heavy metal pollution such as Cd, As, and Pb. At present, the main sources of heavy metals in farmland are atmospheric deposition, the use of pesticides and fertilizers, and sludge fertilization. Heavy metals are difficult to be degraded by microorganisms in the soil. Long-term accumulation will not only have an adverse effect on plant growth, but also pollute groundwater. The ecological and environmental problems caused by the use of fertilizers are becoming increasingly prominent. The irrational use of fertilizers has damaged the soil environment, causing it to harden and reduce its ability to retain water and fertilizer, bringing about adverse environmental impacts.
[0003] At present, the main means of soil remediation include physical, chemical, and biological methods. The purpose of soil remediation is achieved by reducing the content of heavy metals in the soil through adsorption, extraction, transfer, etc. In addition to this method, the use of materials such as remediation agents can also improve the passivation of heavy metals in the soil. The current types of remediation agents mainly include organic / inorganic material remediation agents and composite material remediation agents. Liu Zejun et al. prepared chitosan-based semi-interpenetrating network hydrogels and explored their adsorption process of humic acid, and explored the effects of different influencing factors on adsorption. It provides a reference for its application as an environmentally friendly material and in water treatment. Zhang Yaokun et al. developed an environmentally friendly interpenetrating network alginate gel sphere by chemical cross-linking method, and used it as a new type of phosphorus removal adsorbent, broadening the application of polymer materials in the environmental field. Summary of the invention
[0004] In view of the deficiencies of the prior art, the present invention provides a method for resource utilization of sludge and a method for preparing alginate-protein interpenetrating network fibers, which are achieved through the following technical solutions:
[0005] An alginate-protein interpenetrating network fiber, specifically an alginate-protein semi-interpenetrating network fiber or an alginate-protein fully interpenetrating network fiber, which is prepared by mixing sludge protein, sodium alginate and sludge-based alginate to obtain a raw material, cross-linking the raw material to form a network structure, and preparing it by wet spinning; the water holding capacity of the alginate-protein interpenetrating network fiber is 30% to 90%;
[0006] The raw materials of the alginate-protein semi-interpenetrating network fiber include 100 parts of sludge protein, 0-200 parts of sludge-based alginate, and ≤200 parts of sodium alginate by weight. The raw materials are cross-linked with a calcium chloride solution to form a network structure, and the alginate-protein semi-interpenetrating network fiber is prepared by wet spinning. The diameter of the prepared alginate-protein semi-interpenetrating network fiber is 0.2-1.2 mm, and the surface is smooth. 2+Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-interpenetrating network fibers is 3.0-64.0 MPa, and the breaking elongation is 10.0-73.0%.
[0007] The raw materials of the alginate-protein fully interpenetrating network fiber include 100 parts of sludge protein, 0-200 parts of sludge-based alginate, ≤200 parts of sodium alginate, and ≤100 parts of glutamine transaminase according to weight parts, and the raw materials are cross-linked with calcium chloride solution and glutamine transaminase to form a network structure, and the alginate-protein interpenetrating network fiber is prepared by wet spinning. The diameter of the prepared alginate-protein interpenetrating network fiber is 0.2-1.0 mm, wherein the glutamine transaminase cross-links with the sludge protein to form a network and cross-links with the alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 20.0-146.0 MPa, and the breaking elongation is 8.0-34.0%.
[0008] A method for preparing alginate-protein interpenetrating network fibers comprises the following steps:
[0009] Preparation method of alginate-protein semi-interpenetrating network fiber:
[0010] S1. Dissolve sludge protein in deionized water to obtain a sludge protein solution, add sodium alginate and sludge-based alginate to the solution, and stir to obtain a mixed solution;
[0011] S2. centrifuging the mixed solution obtained in step S1, and obtaining a supernatant as a spinning solution;
[0012] S3. The spinning solution is sucked with a syringe and squeezed into a container filled with calcium chloride solution. After standing for a certain period of time, the calcium chloride solution is poured out, and deionized water is added to completely immerse the spinning solution and soak to obtain a fiber slurry;
[0013] S4. The fiber slurry obtained in step S3 is transferred to anhydrous ethanol for stretching and dried at room temperature to obtain alginate-protein semi-interpenetrating network fibers;
[0014] or:
[0015] Preparation method of alginate-protein fully interpenetrating network fiber:
[0016] S1. Dissolve sludge protein in deionized water to obtain a sludge protein solution, add sodium alginate and sludge-based alginate to the solution, and stir to obtain a mixed solution;
[0017] S2. Adding glutamine transaminase to the mixed solution obtained in S1, and reacting at a certain temperature;
[0018] S3. The solution after the reaction in S2 is placed in a water bath to inactivate the enzyme, and then cooled to room temperature;
[0019] S4. Centrifuging the cooled solution in step S3, and obtaining a supernatant as the spinning solution;
[0020] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with calcium chloride solution. After standing for a certain period of time, the calcium chloride solution is poured out, and deionized water is added to completely immerse the spinning solution and soak to obtain fibers;
[0021] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and dried at room temperature to obtain alginate-protein fully interpenetrating network fiber.
[0022] in:
[0023] In the method for preparing the alginate-protein semi-IPN fiber, in step S1, the concentration of the sludge protein solution is 0.5% to 1% m / v, and the stirring time after mixing is 10 to 15 minutes.
[0024] In the method for preparing the alginate-protein semi-IPN fiber, in step S2, the centrifugal speed is 4500-5000 r / min and the time is 10-15 min.
[0025] In the preparation method of the alginate-protein semi-IPN fiber, in step S3, the concentration w / v of the calcium chloride solution is 10% to 15%, the standing time is not less than 2 hours, and the soaking time after adding deionized water is 1 to 2 minutes.
[0026] In the method for preparing the alginate-protein semi-IPN fiber, in step S4, the length ratio before and after stretching is 1:1.2, and the drying time is not less than 24 hours.
[0027] In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S1, the concentration m / v of the sludge protein solution is 0.5% to 1%, and the stirring time after mixing is 10 to 15 minutes.
[0028] In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S2, the active unit quantity of glutamine aminotransferase in the solution is 10 U / mL, the reaction temperature is 20-25° C., and the reaction time is not less than 2 hours.
[0029] In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S3, the water bath temperature is 90 to 95° C., and the enzyme inactivation time is 5 to 10 minutes.
[0030] In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S4, the centrifugal speed is 4500-5000 r / min, and the time is 10-15 min.
[0031] In the preparation method of the alginate-protein fully interpenetrating network fiber, in step S5, the concentration w / v of the calcium chloride solution is 10% to 15%, the standing time is not less than 2 hours, and the soaking time after adding deionized water is 1 to 2 minutes.
[0032] In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S6, the length ratio before and after stretching is 1:1.2, and the drying time is not less than 24 hours.
[0033] An application of alginate-protein interpenetrating network fiber is used in soil as a medium for improving soil environment.
[0034] Compared with the prior art, the present invention has the following beneficial effects:
[0035] (1) The present invention uses sludge as raw material, which reduces the use of raw materials and saves resources compared with traditional interpenetrating / semi-interpenetrating network fibers.
[0036] (2) Compared with the traditional interpenetrating / semi-interpenetrating network fibers, the alginate-protein interpenetrating network fibers obtained by the present invention have certain mechanical properties and good degradation properties, thereby reducing the pollution to the environment.
[0037] (3) The alginate-protein semi-IPN fibers prepared by the present invention have good breaking stress and breaking elongation due to the hydrophobic interaction and hydrogen bonding between the sludge protein and alginate and the interaction between the carboxyl group of alginate and the white side chain of the sludge protein.
[0038] (4) The alginate-protein fully interpenetrating network fibers prepared by the present invention have good breaking stress and breaking elongation due to the hydrophobic interaction and hydrogen bonding between sludge protein and alginate, as well as the interaction between the carboxyl group of alginate and the side chain of sludge protein. The addition of glutamine aminotransferase makes the bonding between the networks tighter, further enhancing the stretching effect of the fibers.
[0039] (5) The present invention can not only realize the resource utilization of sludge, protein and alginate in sludge, but also realize the reduction of sludge. BRIEF DESCRIPTION OF THE DRAWINGS
[0040] Figure 1Microstructure diagrams of interpenetrating network fibers prepared in Examples 1-10 of the present invention; wherein Figure A is Example 1, Figure B is Example 2, Figure C is Example 3, Figure D is Example 4, Figure E is Example 5, Figure a is Example 6, Figure b is Example 7, Figure c is Example 8, Figure d is Example 9, and Figure e is Example 10;
[0041] Figure 2 Mechanical properties diagram of interpenetrating network fibers prepared in Examples 1-5 of the present invention;
[0042] Figure 3 Mechanical properties diagram of interpenetrating network fibers prepared in Examples 6-10 of the present invention;
[0043] Figure 4 Water holding performance diagram of interpenetrating network fibers prepared in Examples 1-10 of the present invention;
[0044] Figure 5 Sustained release experiment of the interpenetrating network fibers prepared in Examples 1-10 of the present invention. DETAILED DESCRIPTION
[0045] Example 1
[0046] A fully interpenetrating alginate-protein network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein, 0 parts of sludge-based alginate, 200 parts of sodium alginate, and 32 parts of transglutaminase. The raw materials are cross-linked with a calcium chloride solution and transglutaminase to form a network structure, and the fiber is prepared by wet spinning.
[0047] The preparation method of the alginate-protein fully interpenetrating network fiber specifically comprises the following steps:
[0048] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0049] S2. Add glutamine transaminase to the mixed solution obtained in S1 to make the concentration of glutamine transaminase in the solution 10U / mL, and react at 20°C for 2h;
[0050] S3. The solution after the reaction in S2 was placed in a water bath at 90°C for 5 minutes to inactivate the enzyme, and then cooled to room temperature;
[0051] S4. The cooled solution in step S3 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0052] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution is poured out and deionized water is added to completely immerse the spinning solution. The spinning solution is soaked for 1 minute to obtain fibers.
[0053] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein fully interpenetrating network fiber.
[0054] The diameter of the prepared alginate-protein fully interpenetrating network fiber was 0.2 mm, in which glutamine aminotransferase and sludge protein were cross-linked to form a network and bonded with alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 145.3MPa, and the breaking elongation is 33.8%.
[0055] Example 2
[0056] A fully interpenetrating alginate-protein network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein, 100 parts of sludge-based alginate, 100 parts of sodium alginate, and 32 parts of transglutaminase. The raw materials are cross-linked with a calcium chloride solution and transglutaminase to form a network structure, and the fiber is prepared by wet spinning.
[0057] The preparation method of the alginate-protein fully interpenetrating network fiber specifically comprises the following steps:
[0058] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0059] S2. Add glutamine transaminase to the mixed solution obtained in S1 to make the concentration of glutamine transaminase in the solution 10U / mL, and react at 20°C for 2h;
[0060] S3. The solution after the reaction in S2 was placed in a water bath at 90°C for 5 minutes to inactivate the enzyme, and then cooled to room temperature;
[0061] S4. The cooled solution in step S3 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0062] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution is poured out and deionized water is added to completely immerse the spinning solution. The spinning solution is soaked for 1 minute to obtain fibers.
[0063] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein fully interpenetrating network fiber.
[0064] The diameter of the prepared alginate-protein fully interpenetrating network fiber was 0.4 mm, in which glutamine aminotransferase and sludge protein were cross-linked to form a network and combined with alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 68.6MPa, and the breaking elongation is 23.5%.
[0065] Example 3
[0066] A kind of alginate-protein fully interpenetrating network fiber, the raw materials of which, calculated by weight, include 100 parts of sludge protein, 133 parts of sludge-based alginate, 67 parts of sodium alginate, and 32 parts of transglutaminase. The raw materials are cross-linked with calcium chloride solution and transglutaminase to form a network structure, and the fiber is prepared by wet spinning.
[0067] The preparation method of the alginate-protein fully interpenetrating network fiber specifically comprises the following steps:
[0068] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0069] S2. Add glutamine transaminase to the mixed solution obtained in S1 to make the concentration of glutamine transaminase in the solution 10U / mL, and react at 20°C for 2h;
[0070] S3. The solution after the reaction in S2 was placed in a water bath at 90°C for 5 minutes to inactivate the enzyme, and then cooled to room temperature;
[0071] S4. The cooled solution in step S3 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0072] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution is poured out and deionized water is added to completely immerse the spinning solution. The spinning solution is soaked for 1 minute to obtain fibers.
[0073] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein fully interpenetrating network fiber.
[0074] The diameter of the prepared alginate-protein fully interpenetrating network fiber was 1.0 mm, in which glutamine aminotransferase and sludge protein were cross-linked to form a network and bonded with alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 74.2MPa, and the breaking elongation is 15.1%.
[0075] Example 4
[0076] A kind of alginate-protein fully interpenetrating network fiber, the raw materials of which, calculated by weight, include 100 parts of sludge protein, 150 parts of sludge-based alginate, 50 parts of sodium alginate, and 32 parts of transglutaminase. The raw materials are cross-linked with calcium chloride solution and transglutaminase to form a network structure, and the fiber is prepared by wet spinning.
[0077] The preparation method of the alginate-protein fully interpenetrating network fiber specifically comprises the following steps:
[0078] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0079] S2. Add glutamine transaminase to the mixed solution obtained in S1 to make the concentration of glutamine transaminase in the solution 10U / mL, and react at 20°C for 2h;
[0080] S3. The solution after the reaction in S2 was placed in a water bath at 90°C for 5 minutes to inactivate the enzyme, and then cooled to room temperature;
[0081] S4. The cooled solution in step S3 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0082] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution is poured out and deionized water is added to completely immerse the spinning solution. The spinning solution is soaked for 1 minute to obtain fibers.
[0083] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein fully interpenetrating network fiber.
[0084] The diameter of the prepared alginate-protein fully interpenetrating network fiber was 0.8 mm, in which glutamine aminotransferase and sludge protein were cross-linked to form a network and combined with alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 23.4MPa, and the breaking elongation is 8.3%.
[0085] Example 5
[0086] A kind of alginate-protein fully interpenetrating network fiber, the raw materials of which, by weight, include 100 parts of sludge protein, 160 parts of sludge-based alginate, 40 parts of sodium alginate, and 32 parts of transglutaminase. The raw materials are cross-linked with calcium chloride solution and transglutaminase to form a network structure, and the fiber is prepared by wet spinning.
[0087] The preparation method of the alginate-protein fully interpenetrating network fiber specifically comprises the following steps:
[0088] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0089] S2. Add glutamine transaminase to the mixed solution obtained in S1 to make the concentration of glutamine transaminase in the solution 10U / mL, and react at 20°C for 2h;
[0090] S3. The solution after the reaction in S2 was placed in a water bath at 90°C for 5 minutes to inactivate the enzyme, and then cooled to room temperature;
[0091] S4. The cooled solution in step S3 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0092] S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution is poured out and deionized water is added to completely immerse the spinning solution. The spinning solution is soaked for 1 minute to obtain fibers.
[0093] S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein fully interpenetrating network fiber.
[0094] The diameter of the prepared alginate-protein fully interpenetrating network fiber was 0.6 mm, in which glutamine aminotransferase and sludge protein were cross-linked to form a network and combined with alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 30.5MPa, and the breaking elongation is 14.6%.
[0095] Example 6
[0096] An alginate-protein semi-interpenetrating network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein and 200 parts of sodium alginate, is cross-linked with a calcium chloride solution to form a network structure, and is prepared by wet spinning.
[0097] The preparation method of the alginate-protein semi-interpenetrating network fiber specifically comprises the following steps:
[0098] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0099] S2. The solution obtained in step S1 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0100] S3. The spinning solution was sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution was poured out and deionized water was added to completely immerse the spinning solution. The spinning solution was soaked for 1 minute to obtain fibers.
[0101] S4. The fiber obtained in step S3 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein semi-interpenetrating network fiber.
[0102] The diameter of the prepared alginate-protein semi-IPN fiber is 0.2 mm and the surface is smooth. 2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-IPN fiber is 63.8MPa and the breaking elongation is 72.2%.
[0103] Example 7
[0104] An alginate-protein semi-interpenetrating network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein, 100 parts of sodium alginate, and 100 parts of sludge-based alginate. The raw materials are cross-linked with a calcium chloride solution to form a network structure, and the fiber is prepared by wet spinning.
[0105] The preparation method of the alginate-protein semi-interpenetrating network fiber specifically comprises the following steps:
[0106] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0107] S2. The solution obtained in step S1 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0108] S3. The spinning solution was sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution was poured out and deionized water was added to completely immerse the spinning solution. The spinning solution was soaked for 1 minute to obtain fibers.
[0109] S4. The fiber obtained in step S3 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein semi-interpenetrating network fiber.
[0110] The diameter of the prepared alginate-protein semi-IPN fiber was 1.0 mm and the surface was smooth. 2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-IPN fiber is 21.4MPa and the breaking elongation is 47.3%.
[0111] Example 8
[0112] A kind of alginate-protein semi-interpenetrating network fiber, the raw materials of which, by weight, include 100 parts of sludge protein, 67 parts of sodium alginate and 133 parts of sludge-based alginate, and the raw materials are cross-linked with calcium chloride solution to form a network structure, and the fiber is prepared by wet spinning.
[0113] The preparation method of the alginate-protein semi-interpenetrating network fiber specifically comprises the following steps:
[0114] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0115] S2. The solution obtained in step S1 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0116] S3. The spinning solution was sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution was poured out and deionized water was added to completely immerse the spinning solution. The spinning solution was soaked for 1 minute to obtain fibers.
[0117] S4. The fiber obtained in step S3 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein semi-interpenetrating network fiber.
[0118] The diameter of the prepared alginate-protein semi-IPN fiber was 1.0 mm and the surface was smooth.2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-IPN fiber is 17.8MPa and the breaking elongation is 21.5%.
[0119] Example 9
[0120] An alginate-protein semi-interpenetrating network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein, 50 parts of sodium alginate, and 150 parts of sludge-based alginate. The raw materials are cross-linked with a calcium chloride solution to form a network structure, and the fiber is prepared by wet spinning.
[0121] The preparation method of the alginate-protein semi-interpenetrating network fiber specifically comprises the following steps:
[0122] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0123] S2. The solution obtained in step S1 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0124] S3. The spinning solution was sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution was poured out and deionized water was added to completely immerse the spinning solution. The spinning solution was soaked for 1 minute to obtain fibers.
[0125] S4. The fiber obtained in step S3 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein semi-interpenetrating network fiber.
[0126] The diameter of the prepared alginate-protein semi-IPN fiber is 0.6 mm and the surface is smooth. 2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-interpenetrating network fiber is 3.2MPa and the breaking elongation is 10.8%.
[0127] Example 10
[0128] An alginate-protein semi-interpenetrating network fiber, whose raw materials, measured by weight, include 100 parts of sludge protein, 40 parts of sodium alginate, and 160 parts of sludge-based alginate. The raw materials are cross-linked with a calcium chloride solution to form a network structure, and the fiber is prepared by wet spinning.
[0129] The preparation method of the alginate-protein semi-interpenetrating network fiber specifically comprises the following steps:
[0130] S1. Dissolve the sludge protein in deionized water and adjust the volume to 50 mL to a concentration (m / v) of 0.5% to obtain a sludge protein solution. Add sodium alginate to the solution, mix, and stir magnetically for 15 min to obtain a mixed solution.
[0131] S2. The solution obtained in step S1 is centrifuged at 5000 r / min for 15 min, and the resulting supernatant is the spinning solution;
[0132] S3. The spinning solution was sucked with a syringe and squeezed into a culture dish filled with a calcium chloride solution with a w / v concentration of 15%. After standing for 2 hours, the calcium chloride solution was poured out and deionized water was added to completely immerse the spinning solution. The spinning solution was soaked for 1 minute to obtain fibers.
[0133] S4. The fiber obtained in step S3 is transferred to anhydrous ethanol for stretching, and the length ratio before and after stretching is 1:1.2. The fiber is dried at room temperature for 24 hours to obtain alginate-protein semi-interpenetrating network fiber.
[0134] The diameter of the prepared alginate-protein semi-IPN fiber was 1.2 mm and the surface was smooth. 2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-IPN fiber is 9.8MPa and the breaking elongation is 23.2%.
[0135] The microstructure of the interpenetrating network fibers prepared in Examples 1-10 was observed using an optical microscope at 40 times magnification. Figure 1 As shown, the fibers prepared in each embodiment have the basic fiber shape and a smooth surface. The fully interpenetrating network fibers and semi-interpenetrating network fibers prepared by pure sodium alginate in embodiments 1 and 6 are the thinnest, with a diameter of 0.2 mm, and the diameters of the two fibers prepared by doping in other proportions are all above 0.5 mm.
[0136] The mechanical properties of the protein-alginate fully interpenetrating network fibers prepared in Examples 1-5 are as follows: Figure 2 As shown, the mechanical properties of the protein-alginate semi-IPN fibers prepared in Examples 6-10 are as follows Figure 3As shown. The breaking stress and breaking elongation of the interpenetrating network fiber gradually decreased when the doping ratio of pure sodium alginate and sludge protein was mixed to pure sodium alginate and sludge-based alginate was 3:1, and increased when the doping ratio was 4:1. As the doping ratio increased, the purity of the extracted sludge-based alginate was only about 50%, which may make its compatibility with sludge protein worse, thereby reducing the uniformity and continuity of the fiber and reducing the breaking stress. The increase in the doping ratio means that more sludge-based alginate is mixed in, which will affect the interaction between sludge-based alginate and Ca 2+ The network structure of the sludge-based alginate network system reduces the molecular fluidity and flexibility, which in turn leads to a decrease in the elongation at break of the two fibers. Overall, the fracture stress and elongation at break of the fully interpenetrating network fiber are higher than those of the semi-interpenetrating network fiber. This is because the addition of glutamine transaminase makes the network more tightly bound, thus enhancing the tensile effect of the fiber, making it less likely to break than the semi-interpenetrating network.
[0137] The water holding performance of the alginate-protein interpenetrating network fibers prepared in Examples 1-10 is shown in FIG. Figure 4 As shown in the figure, the water holding capacity of both the fully interpenetrating network fiber and the semi-interpenetrating network fiber decreases with the increase of the doping ratio. The water holding capacity of the fiber prepared by sodium alginate can reach more than 80%. At the same doping ratio, the water holding capacity of the fully interpenetrating network fiber is higher than that of the semi-interpenetrating network fiber, which is caused by the tighter double network structure formed by the interpenetrating network structure.
[0138] The water holding rate of the alginate-protein interpenetrating network fiber prepared by the present invention is between 30% and 90%. It can be seen that although the raw materials of the two fibers prepared in this study are taken from sludge and the purity is slightly lower than that of commercially available sodium alginate and bovine serum albumin, they still have good water holding performance and can meet the conditions for their application in the slow-release medium of agricultural fertilizers and pesticides.
[0139] The alginate-protein interpenetrating network fibers prepared in Examples 2 and 7 were subjected to sustained release experiments. The results are as follows: Figure 5 , as shown in Table 1. The concentration of phosphate ions in the spinning solution is 0.24 mg / dL. Figure 5 It can be seen that the sustained release capacity of the two fibers increased steadily from 0 to 24 hours, reaching the highest point at 24 hours. At this time, the fully interpenetrating network fiber released 0.025 mg / dL of phosphate, and the semi-interpenetrating network fiber released 0.063 mg / dL of phosphate. Both of the prepared fibers can be used as long-term sustained releasers of phosphate ions in the aqueous phase. If used in soil, the sustained release period may be longer.
[0140] Table 1 Absorbance of phosphate ions released by alginate-protein interpenetrating networks (mg / dL)
[0141]
Claims
1. An alginate-protein interpenetrating network fiber, characterized in that: Specifically, it is alginate-protein semi-interpenetrating network fiber or alginate-protein fully interpenetrating network fiber, which is prepared by mixing sludge protein, sodium alginate and sludge-based alginate as raw materials, cross-linking the raw materials to form a network structure, and preparing it by wet spinning; the water holding capacity of the alginate-protein interpenetrating network fiber is 30% to 90%.
2. The alginate-protein interpenetrating network fiber according to claim 1, characterized in that: The raw materials of the alginate-protein semi-interpenetrating network fiber include 100 parts of sludge protein, 0-200 parts of sludge-based alginate, and ≤200 parts of sodium alginate by weight. The raw materials are cross-linked with a calcium chloride solution to form a network structure, and the alginate-protein semi-interpenetrating network fiber is prepared by wet spinning. The diameter of the prepared alginate-protein semi-interpenetrating network fiber is 0.2-1.2 mm, and the surface is smooth. 2+ Combined to form a tight network, sludge proteins are randomly distributed in alginate and Ca 2+ In the eggshell network formed by interweaving, the breaking stress of the semi-interpenetrating network fibers is 3.0-64.0 MPa, and the breaking elongation is 10.0-73.0%.
3. The alginate-protein interpenetrating network fiber according to claim 1, characterized in that: The raw materials of the alginate-protein fully interpenetrating network fiber include 100 parts of sludge protein, 0-200 parts of sludge-based alginate, ≤200 parts of sodium alginate, and ≤100 parts of glutamine transaminase according to weight parts, and the raw materials are cross-linked with calcium chloride solution and glutamine transaminase to form a network structure, and the alginate-protein interpenetrating network fiber is prepared by wet spinning. The diameter of the prepared alginate-protein interpenetrating network fiber is 0.2-1.0 mm, wherein the glutamine transaminase cross-links with the sludge protein to form a network and cross-links with the alginate-Ca 2+ The network is interwoven, and the breaking stress of the fully interpenetrating network fiber is 20.0-146.0 MPa, and the breaking elongation is 8.0-34.0%.
4. The method for preparing the alginate-protein interpenetrating network fiber according to claim 1, characterized in that: The specific steps include: Preparation method of alginate-protein semi-interpenetrating network fiber: S1. Dissolve sludge protein in deionized water to obtain a sludge protein solution, add sodium alginate and sludge-based alginate to the solution, and stir to obtain a mixed solution; S2. centrifuging the mixed solution obtained in step S1, and obtaining a supernatant as a spinning solution; S3. The spinning solution is sucked with a syringe and squeezed into a container filled with calcium chloride solution. After standing for a certain period of time, the calcium chloride solution is poured out, and deionized water is added to completely immerse the spinning solution and soak to obtain a fiber slurry; S4. The fiber slurry obtained in step S3 is transferred to anhydrous ethanol for stretching and dried at room temperature to obtain alginate-protein semi-interpenetrating network fibers; or: Preparation method of alginate-protein fully interpenetrating network fiber: S1. Dissolve sludge protein in deionized water to obtain a sludge protein solution, add sodium alginate and sludge-based alginate to the solution, and stir to obtain a mixed solution; S2. Adding glutamine transaminase to the mixed solution obtained in S1, and reacting at a certain temperature; S3. The solution after the reaction in S2 is placed in a water bath to inactivate the enzyme, and then cooled to room temperature; S4. Centrifuging the cooled solution in step S3, and obtaining a supernatant as the spinning solution; S5. The spinning solution is sucked with a syringe and squeezed into a culture dish filled with calcium chloride solution. After standing for a certain period of time, the calcium chloride solution is poured out, and deionized water is added to completely immerse the spinning solution and soak to obtain fibers; S6. The fiber obtained in step S5 is transferred to anhydrous ethanol for stretching, and dried at room temperature to obtain alginate-protein fully interpenetrating network fiber.
5. The method for preparing alginate-protein interpenetrating network fiber according to claim 4, characterized in that: In the preparation method of the alginate-protein semi-IPN fiber, in step S1, the concentration of the sludge protein solution is 0.5% to 1% m / v, and the stirring time after mixing is 10 to 15 minutes; In the method for preparing the alginate-protein semi-IPN fiber, in step S2, the centrifugal speed is 4500-5000 r / min and the time is 10-15 min.
6. The method for preparing an alginate-protein interpenetrating network fiber according to claim 4, characterized in that: In the preparation method of the alginate-protein semi-IPN fiber, in step S3, the concentration w / v of the calcium chloride solution is 10% to 15%, the standing time is not less than 2 hours, and the soaking time after adding deionized water is 1 to 2 minutes; In the method for preparing the alginate-protein semi-IPN fiber, in step S4, the length ratio before and after stretching is 1:1.2, and the drying time is not less than 24 hours.
7. The method for preparing alginate-protein interpenetrating network fiber according to claim 4, characterized in that: In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S1, the concentration m / v of the sludge protein solution is 0.5% to 1%, and the stirring time after mixing is 10 to 15 minutes.
8. The method for preparing alginate-protein interpenetrating network fiber according to claim 4, characterized in that: In the preparation method of the alginate-protein fully interpenetrating network fiber, in step S2, the active unit quantity of glutamine aminotransferase in the solution is 10U / mL, the reaction temperature is 20-25°C, and the reaction time is not less than 2h; In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S3, the water bath temperature is 90 to 95° C., and the enzyme inactivation time is 5 to 10 minutes.
9. The method for preparing alginate-protein interpenetrating network fiber according to claim 4, characterized in that: In the method for preparing alginate-protein fully interpenetrating network fibers, in step S4, the centrifugal speed is 4500-5000 r / min, and the time is 10-15 min; In the preparation method of the alginate-protein fully interpenetrating network fiber, in step S5, the concentration w / v of the calcium chloride solution is 10% to 15%, the standing time is not less than 2 hours, and the soaking time after adding deionized water is 1 to 2 minutes; In the method for preparing the alginate-protein fully interpenetrating network fiber, in step S6, the length ratio before and after stretching is 1:1.2, and the drying time is not less than 24 hours.
10. The use of an alginate-protein interpenetrating network fiber according to claim 1, characterized in that: Used in soil as a medium to improve soil environment.