Preparation method and application of cement-based material biomass antifreeze agent
By combining physical and chemical methods to modify cod antifreeze protein, the problem of its reduced activity in high-salt and high-alkali environments is solved, efficient application in these environments is achieved, and the freezing rate and freezing point are significantly reduced.
Patent Information
- Application Number
- CN202510015620.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-03
- Publication Date
- 2025-04-11
AI Technical Summary
Antifreeze protein is susceptible to factors such as pH, temperature, osmotic pressure, salt concentration and other factors in high-salt and high-alkali environments, resulting in structural changes and reduced activity, limiting its application in engineering construction.
New methods combined with physical and chemical methods are used to modify cod antifreeze protein, and the activity of antifreeze protein is improved by mixing reflux and degreasing with solvents and compounding with surfactants.
It effectively improves the activity of antifreeze protein, expands its application range in high-salt and high-alkali environments, and can significantly reduce the freezing rate and freezing point in pure water and ion-containing solutions.
Smart Images
Figure CN119797799A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of antifreeze concrete preparation, and in particular to a preparation method and application of a cement-based biomass antifreeze agent. Background Art
[0002] Ice is a natural phenomenon that widely exists in life. It is easy to occur when the temperature is low and the humidity is high. The formation and accumulation of ice often bring adverse effects and great inconvenience to various aspects of human production and life. Especially when it occurs in some infrastructure materials, it will cause some major accidents.
[0003] Antifreeze protein, an antifreeze agent derived from organisms, has attracted much attention in the field of antifreeze research because of its trace efficiency and multi-faceted characteristics of inhibiting ice nucleation and preventing ice crystal growth. Antifreeze protein can lower the freezing point, interact with ice crystals and combine with them, effectively inhibiting the lowering of the freezing point, inhibiting recrystallization and modifying the morphology of ice crystals.
[0004] Currently, there is little research on antifreeze proteins in some extreme environments, such as the high-salt and high-alkali environments in engineering construction. The fundamental reason is that antifreeze proteins are easily affected by pH, temperature, osmotic pressure, salt concentration, etc. in the above environments, resulting in structural changes that affect the normal performance of their activity.
[0005] At present, there are few studies on the specific modification methods of antifreeze proteins. Therefore, it is planned to start from common protein modification methods and develop a new method that combines physical and chemical methods to modify antifreeze proteins. This can further expand the application of antifreeze proteins and establish a programmed method for protein to engineering applications. Summary of the invention
[0006] The purpose of the present invention is to provide a preparation method and application of a cement-based biomass antifreeze agent.
[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0008] The present invention provides a method for preparing a biomass concrete antifreeze agent, comprising the following steps:
[0009] (1) mixing cod antifreeze protein with a solvent and refluxing to defatted to obtain defatted protein;
[0010] (2) mixing the delipidated protein with a solvent to obtain a delipidated protein solution;
[0011] (3) Mixing the defatted protein solution with a surfactant solution to obtain a biomass concrete antifreeze agent.
[0012] Preferably, in step (1), the mass volume ratio of the cod antifreeze protein to the solvent is 10-20 g:100 ml; and the solvent is one or more of petroleum ether, ether and ethanol.
[0013] Preferably, the reflux temperature in step (1) is 10 to 85° C., the time is 1 to 3 hours, and the number of reflux times is 3 to 10 times.
[0014] Preferably, the concentration of the delipidated protein solution in step (2) is 0.1 to 30 mg / ml.
[0015] Preferably, the surfactant solution in step (2) comprises solution A and solution B; solution A is an SDS solution; solution B is a DTAB or CTAB solution; and the volume ratio of solution A to solution B is 1-5:1-10.
[0016] Preferably, the concentration of solution A in step (2) is 0.005×10 -3 ~1.0mol / l; the concentration of solution B is 0.005×10 -3 ~1.0mol / l.
[0017] Preferably, the volume ratio of the delipidated protein solution to the surfactant solution in step (2) is 1-4:1-4.
[0018] The invention also provides a biomass concrete antifreeze agent prepared by the preparation method.
[0019] The invention also provides application of the biomass concrete antifreeze agent in preparing high-freeze-resistant concrete.
[0020] Preferably, the mass ratio of the biomass concrete antifreeze agent added to the high frost resistance concrete is 0.03-0.3%.
[0021] In the present invention, the cod antifreeze protein is selected from deep-sea cod and purchased from Shanghai Naijin Industrial Co., Ltd.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] The present invention discloses a method for preparing a protein antifreeze agent, which expands the application scope of biomass antifreeze agents. The target antifreeze agent is obtained by extraction using an alkali method, followed by purification and defatting. The purpose of defatting is that the presence of fat affects the stability of the system, interfacial activity and other problems in the subsequent process of modifying the antifreeze protein using a surfactant. The present invention compounded the defatted cod antifreeze protein with solution A: anionic surfactant (SDS) and solution B: cationic ion surfactant (such as DTAB, CTAB, etc.) with different concentrations, and modified the antifreeze active protein with a surfactant composite system, thereby changing the state and charge of the protein in the solution and improving the activity of the antifreeze protein. Compared with other modification methods, this method is easy to operate and has significant effects.
[0024] The protein-surfactant composite system of the present invention has a good effect of reducing the frost heave damage of the solution. It can change the morphology of the ice crystals of the solution and reduce the freezing point of the solution. In the pure water solution, the frost heave rate of the system is reduced by 13.9%, and the freezing point is reduced by 5°C. 2+ Mg 2+ 、Na + , K + 、SO4 2- , Cl - It can still effectively exert antifreeze activity in solutions with an ion pH of 8 to 12, which expands the practical application of antifreeze proteins in agricultural engineering, construction facilities and various materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.
[0026] Figure 1 The antifreeze activity of Pro-SDS-DTAB system in aqueous solution; the change of frost heave rate at different concentrations of Pro-SDS-DTAB in water system.
[0027] Figure 2 Antifreeze activity of Pro-SDS-DTAB system in aqueous solution; freezing point change diagram.
[0028] Figure 3 The antifreeze activity of Pro-SDS-CTAB system in aqueous solution; the change of frost heave rate at different concentrations of Pro-SDS-CTAB in water system.
[0029] Figure 4Antifreeze activity of Pro-SDS-CTAB system in aqueous solution; freezing point change diagram.
[0030] Figure 5 The change of freeze heave rate of different concentrations of hydration water Pro-SDS-CTAB.
[0031] Figure 6 is the mortar frost heave rate. DETAILED DESCRIPTION
[0032] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0033] Example 1
[0034] A method for preparing a biomass concrete antifreeze agent, comprising the following steps:
[0035] (1) Codfish antifreeze protein and a solvent are mixed and refluxed for defatting to obtain defatted protein; the mass volume ratio of the codfish antifreeze protein to the solvent is 10 g:100 ml; the solvent is petroleum ether; the reflux temperature is 10° C., the time is 1 hour, and the number of refluxes is 3 times.
[0036] (2) mixing the delipidated protein with water to obtain a delipidated protein solution having a concentration of 0.1 mg / ml;
[0037] (3) The delipidated protein solution and the surfactant solution are mixed in a volume ratio of 4:1 to obtain a biomass concrete antifreeze agent; the surfactant solution includes solution A and solution B in a volume ratio of 5:1; the solution A is an SDS solution; the solution B is a DTAB solution; the concentration of the solution A is 0.005×10 -3 mol / l; the concentration of solution B is 0.005×10 -3 mol / l.
[0038] Example 2
[0039] A method for preparing a biomass concrete antifreeze agent, comprising the following steps:
[0040] (1) Codfish antifreeze protein and a solvent are mixed and refluxed for defatting to obtain defatted protein; the mass volume ratio of the codfish antifreeze protein to the solvent is 20 g:100 ml; the solvent is ether; the reflux temperature is 85° C., the time is 3 h; and the number of refluxes is 10 times.
[0041] (2) mixing the delipidated protein with water to obtain a delipidated protein solution having a concentration of 30 mg / ml;
[0042] (3) The delipidated protein solution and the surfactant solution are mixed in a volume ratio of 4:1 to obtain a biomass concrete antifreeze agent; the surfactant solution includes solution A and solution B in a volume ratio of 5:10; the solution A is an SDS solution; the solution B is a CTAB solution; the concentration of the solution A is 1.0 mol / l; the concentration of the solution B is 1.0 mol / l.
[0043] Example 3
[0044] A method for preparing a biomass concrete antifreeze agent, comprising the following steps:
[0045] (1) Codfish antifreeze protein and a solvent are mixed and refluxed for defatting to obtain defatted protein; the mass volume ratio of the codfish antifreeze protein to the solvent is 10 g:100 ml; the solvent is petroleum ether; the reflux temperature is 60° C., the time is 2 h; and the number of refluxes is 8 times.
[0046] (2) mixing the delipidated protein with water to obtain a delipidated protein solution having a concentration of 2 mg / ml;
[0047] (3) The delipidated protein solution and the surfactant solution are mixed in a volume ratio of 1:1 to obtain a biomass concrete antifreeze agent; the surfactant solution includes solution A and solution B in a volume ratio of 1:1; the solution A is an SDS solution; the solution B is a DTAB solution; the concentration of the solution A is 1.0 mol / l; the concentration of the solution B is 1.0 mol / l.
[0048] Example 4
[0049] A method for preparing a biomass concrete antifreeze agent, comprising the following steps:
[0050] (1) Codfish antifreeze protein and a solvent are mixed and refluxed for defatting to obtain defatted protein; the mass volume ratio of the codfish antifreeze protein to the solvent is 10 g:100 ml; the solvent is petroleum ether; the reflux temperature is 60° C., the time is 2 h; and the number of refluxes is 8 times.
[0051] (2) mixing the delipidated protein with water to obtain a delipidated protein solution having a concentration of 2 mg / ml;
[0052] (3) The delipidated protein solution and the surfactant solution are mixed in a volume ratio of 1:1 to obtain a biomass concrete antifreeze agent; the surfactant solution includes solution A and solution B in a volume ratio of 1:1; the solution A is an SDS solution; the solution B is a CTAB solution; the concentration of the solution A is 1.0 mol / l; the concentration of the solution B is 1.0 mol / l.
[0053] Experimental Example 1
[0054] In a low temperature constant temperature water bath at -20°C, the biomass concrete antifreeze agent obtained in Example 3 was measured. The maximum frost heave rate and the freezing point of the measurement system under different ratios of solution A and solution B were characterized by changes in antifreeze activity; the protein solution (without surfactant) was used as the control group. The results are as follows Figure 1 and 2 As shown, the frost heave rate of the product obtained in Example 3 is lower than that of pure water, with a maximum reduction of 13.9%, and the freezing point is reduced by 5°C.
[0055] In a low-temperature water bath, the biomass concrete antifreeze agent obtained in Example 4 was measured. The maximum frost heave rate and the freezing point of the system under different ratios of solution A and solution B were used to characterize the changes in antifreeze activity. The pure protein solution was used as the control group. The results are as follows Figure 3 and 4 As shown, the frost heave rate of the product obtained in Example 4 is lower than that of pure water, with a maximum reduction of 17.5%, and the freezing point is reduced by 8° C. Table 1 records the settings of different proportions of solution A and solution B.
[0056] Table 1. Protein-surfactant system ratio 1
[0057]
[0058] Experimental Example 2
[0059] The product obtained in Example 3 was added to cement hydration water at a water-cement ratio (w / c 0.5) (cement and water were stirred at a ratio of 10:1 at 800 rpm for 1 h, and then the cement paste was filtered to obtain cement hydration water, pH = 10.5, containing Ca 2+ Mg 2+ 、Na + , K + , Cl - The effects of different ratios of solution A and solution B on the maximum frost heave rate were determined in plasma. The results are shown in Figure 5 As shown, the maximum decrease in the frost heave rate of the solution is 9.7%.
[0060] The product obtained in Example 3 was added into cement mortar prepared according to the standard of GB / T1761-2021 at a water-cement ratio (w / c 0.5) and the frost heave rates of cement mortars with different proportions of solution A and solution B at low temperature were measured. The results are as follows: Figure 6 As shown, it shows that the anti-frost heave activity of the mortar increases, and its frost heave rate decreases by 10.5% to 38.1%. Table 2 records the different ratio settings of solution A and solution B.
[0061] Table 2. Protein-surfactant system ratio 2
[0062]
[0063] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A method for preparing a biomass concrete antifreeze agent, characterized in that: The steps include: (1) mixing cod antifreeze protein with a solvent and refluxing to defatted to obtain defatted protein; (2) mixing the delipidated protein with a solvent to obtain a delipidated protein solution; (3) Mixing the defatted protein solution with a surfactant solution to obtain a biomass concrete antifreeze agent.
2. The preparation method according to claim 1, characterized in that: In step (1), the mass volume ratio of the cod antifreeze protein to the solvent is 10-20 g:100 ml; the solvent is one or more of petroleum ether, ether and ethanol.
3. The preparation method according to claim 1, characterized in that: The reflux temperature in step (1) is 30 to 85° C., and the time is 1 to 3 hours; the reflux frequency is 3 to 10 times.
4. The preparation method according to claim 1, characterized in that: The concentration of the delipidated protein solution in step (2) is 0.1 to 30 mg / ml.
5. The preparation method according to claim 1, characterized in that: The surfactant solution in step (2) comprises solution A and solution B; solution A is an SDS solution; solution B is a DTAB or CTAB solution; and the volume ratio of solution A to solution B is 1-5:1-10.
6. The preparation method according to claim 5, characterized in that: The concentration of solution A in step (2) is 0.005×10 -3 ~1.0mol / l; the concentration of solution B is 0.005×10 -3 ~1.0mol / l.
7. The preparation method according to claim 1, characterized in that: The volume ratio of the delipidated protein solution to the surfactant solution in step (2) is 1-4:1-4.
8. The biomass concrete antifreeze agent prepared by the preparation method according to any one of claims 1 to 7.
9. Use of the biomass concrete antifreeze agent according to claim 8 in the preparation of high frost-resistant concrete.
10. The use according to claim 9, characterized in that: The mass proportion of the biomass concrete antifreeze agent added to the high antifreeze concrete is 0.03-0.3%.