Method for promoting degradation of penicillin antibiotics in water body

Abstract

The invention discloses a method for promoting degradation of penicillin antibiotics in a water body. The method comprises the following steps: S1, detecting water quality; s2, medium adjustment; s3, carrying out catalytic degradation; s4, precipitation reaction; medium adjustment is performed on the water body to be treated by using calcium ions and organic matters, so that an example state in the water body to be treated is good, the calcium ions can be coordinated with carbonyl and carboxyl in penicillin molecules, a hydrolyzed reaction intermediate is stabilized, the hydrolysis rate of penicillin antibiotics is increased, and the yield of penicillin antibiotics is increased. The characteristic functional groups such as amino and sulfydryl in the biological metabolism organic matter can also serve as strong nucleophilic reagents to promote rapid hydrolysis of penicillin antibiotics, and meanwhile, through specific setting of the method, it can be avoided that calcium ions and biological organic metabolism media cause secondary pollution to the to-be-treated water body before degradation.

Description

Technical Field

[0001] The invention relates to the technical field of water treatment, in particular to a method for promoting the degradation of penicillin antibiotics in water. Background Art

[0002] Penicillin G (PG), as an important broad-spectrum penicillin antibiotic, has been widely used in the prevention and treatment of human and livestock diseases. However, penicillin antibiotics have a short half-life in the body, and most of the antibiotic precursors are excreted from the body through urine and feces through the body circulation and discharged into the environmental water. For example, Clarke's research shows that 30% of oral and 75% of intravenous ampicillin precursors are not absorbed by the human body and are directly excreted through urine (Mitchell et al. 2014). In addition, a large number of precursors of various antibiotics such as penicillin are also present in untreated wastewater from pharmaceutical companies, which can also enter environmental water bodies through sewage; the discharge of penicillin G and other antibiotics into water bodies may cause bacteria to develop drug resistance, which not only affects the efficacy of antibiotics, but may also lead to an increase in refractory infections. At the same time, it destroys the ecological balance. The presence of antibiotics may interfere with the normal physiological functions of aquatic organisms, affect their growth and reproduction, and thus destroy the balance of the aquatic ecosystem. The presence of antibiotics may reduce the water quality of the water body, affect the survival of aquatic organisms and human drinking water safety. In addition, the selective inhibition of sensitive microorganisms by antibiotics may lead to a reduction in the diversity of microorganisms in the water body, thereby affecting the functions and services of the entire ecosystem.

[0003] In the prior art, penicillin antibiotics are relatively stable in water environments and are not easily degraded naturally, which allows them to exist in water bodies for a long time. In addition, penicillin antibiotics have a certain resistance to conventional chemical oxidants (such as chlorine and ozone), which limits the application of chemical oxidation methods in degrading these antibiotics. At the same time, penicillin antibiotics have a certain resistance to the photolysis of ultraviolet and visible light, which reduces the efficiency of photocatalytic degradation. Penicillin antibiotics may also adsorb suspended particles and sediments in water bodies, making them difficult to remove by traditional water treatment methods. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a method for promoting the degradation of penicillins in water.

[0005] A method for promoting the degradation of penicillin antibiotics in water, comprising the following steps:

[0006] S1. Water quality testing;

[0007] Detection of penicillin antibiotic concentration and Ca in water 2+Parameters of concentration, DO and COD;

[0008] S2, medium adjustment;

[0009] Regulation of Ca 2+ Concentration, when Ca in water 2+ The concentration is less than Ca 2+ When the minimum value of the set threshold is reached, calcium-containing substances are added to the water body until Ca 2+ When the concentration reaches the set threshold, 2+ When the concentration is greater than the maximum value of the set threshold, ion exchange resin or lime softening method is used to remove excess Ca 2+ To Ca 2+ The concentration reaches the set threshold;

[0010] When the DO and COD in the water body are not over the limit, add biological metabolizable organic matter to the water body until the concentration of biological metabolizable organic matter is 10-50 mg / L;

[0011] S3, catalytic degradation;

[0012] Add photocatalytic material to water at a concentration of 0.1-1 g / L and disperse; then adjust the pH to 6.5-7.5, control the water temperature at 15-25°C, and stir at a speed of 40-80 rpm to perform a hydrolysis reaction; at the same time, irradiate the water with ultraviolet light at an intensity of 10-20 mW / cm 2 , irradiation time is 2 to 4 hours;

[0013] S4, precipitation reaction;

[0014] Add 10-15% of the volume fraction of cells to the water body with a density of 1×10 6 cells / mL of Spirulina: then maintain the CO2 concentration in the water at 5-10 mM by adding NaHCO3 or passing CO2 gas; then adjust the pH value to 8.5-9.0, start stirring and then add 10 mg / L polyacrylamide with a volume fraction of 5-7% as a flocculant, the stirring speed is 100-150 rpm, the stirring time is 30-40 min, and then solid-liquid separation is carried out after precipitation for 1 hour, and the degradation is completed.

[0015] Description: The above method can make the sample in the water to be treated in good condition by adjusting the medium of the water to be treated by using calcium ions and organic matter. Since calcium ions can coordinate with the carbonyl and carboxyl groups in the penicillin molecule, stabilize the hydrolysis reaction intermediates and accelerate the hydrolysis rate of penicillin antibiotics. The characteristic functional groups such as amino and thiol in the biological metabolic organic matter can also act as strong nucleophiles to promote the rapid hydrolysis of penicillin antibiotics. However, the direct use of calcium ions and biological metabolic organic media may cause the complexity of the water body and secondary pollution. Through the above threshold range and judgment method, it can be ensured that calcium ions and biological organic metabolic media do not cause secondary pollution to the water to be treated before degradation.

[0016] Furthermore, the set threshold is 50-100 mg / L.

[0017] Note: The above-mentioned threshold setting range has a good effect in promoting the degradation of antibiotics.

[0018] Furthermore, the standard that both DO and COD in the water body do not exceed the standard is the existing surface water environmental quality standard.

[0019] Note: Specifically, the existing surface water environmental quality standards refer to the indicators of the three types of water bodies in GB 3838-2002.

[0020] Furthermore, the calcium-containing substance is calcium ion-doped nano-hydroxyapatite; the preparation method of the calcium ion-doped nano-hydroxyapatite is:

[0021] S1-1, firstly, CaCl2 and SrCl2 are mixed and dissolved in deionized water according to 8-10 mmol: 1 mmol: 100 mL to obtain a first mixed solution;

[0022] S1-2, adding a phosphoric acid solution with a mass concentration of 20-30% to the first mixed solution while stirring until the pH value is 7-9 to obtain a second mixed solution; the dropping speed is 0.5-1 mL / s; the stirring speed is 500-600 rpm;

[0023] S1-3, under continuous stirring, slowly dropwise adding ammonia water or sodium hydroxide into the second mixed solution to adjust the pH value to 10; then aging the second mixed solution for 12 to 15 hours to obtain a suspension;

[0024] S1-4, centrifuging the suspension to obtain a supernatant and a precipitate, removing the supernatant, washing the precipitate with deionized water, and drying the washed precipitate to obtain a dried powder;

[0025] S1-5, calcining the dried powder at 400-500° C. for 2-3 hours to obtain calcium ion-doped nano-hydroxyapatite.

[0026] Description: The dissolution equilibrium of the above-mentioned calcium ion-doped nanohydroxyapatite in water will lead to the gradual release of calcium ions; under a certain pH value and ionic strength, the calcium ions on the surface of the nanohydroxyapatite can be exchanged with other ions in the water, thereby being released into the water body; and the microorganisms in the water body promote its dissolution and the release of calcium ions; the calcium ion-doped nanohydroxyapatite has good biocompatibility, has little effect on the organisms in the water body and can continuously and stably release calcium ions, maintain the calcium ion concentration of the water body, is beneficial to the long-term stability of the water quality, and avoids new pollution during the water treatment process. In addition to releasing calcium ions, nanohydroxyapatite can also adsorb and aggregate heavy metal ions and other pollutants in the water through its porous structure and large specific surface area, thereby promoting the degradation process.

[0027] Furthermore, the aging treatment is: subjecting the second mixed liquid to a gradient change in temperature within a range of 10° C. to 40° C.

[0028] Note: The above temperature gradient change can promote crystal growth to improve its crystallinity and stability.

[0029] Furthermore, the temperature of the second mixed liquid is gradually changed within 10°C to 40°C: after the temperature of the second mixed liquid is reduced to 10°C, it is heated to 40°C after 1 to 2 hours, then maintained for 10 minutes, and then cooled to 10°C for 1 to 2 hours, and the heating and cooling are repeated until the treatment is completed.

[0030] Furthermore, the preparation method of the biological metabolic organic matter is:

[0031] First, the corn stalks are cut into small segments of 2-5 cm; they are softened by steam or water soaking to obtain softened stalks;

[0032] Then, the softened straw is mixed with a composite fermentation agent, wherein the inoculation amount of the composite fermentation agent is 1 to 5% of the weight of the straw; and molasses accounting for 5 to 10% of the weight of the straw is added;

[0033] The inoculated softened straw is then piled into compost, fermented at 30-40°C, the pH is adjusted to 6.0-7.5, and fermented for 4-6 weeks, with the pile turned every week; after the fermentation is completed, biological metabolic organic matter is obtained.

[0034] Note: The characteristic functional groups such as amino and thiol in the biological metabolic organic matter prepared by the above method can also be used as strong nucleophilic reagents to promote the rapid hydrolysis of penicillin antibiotics. At the same time, the preparation of biological metabolic organic matter using corn stalks and composite bacterial agents can realize resource recycling, and through biological metabolism into organic matter, it realizes the resource utilization of waste and reduces environmental pollution. It has a relatively low impact on the environment.

[0035] Furthermore, the composite fermentation bacterial agent includes two or more of Bacillus subtilis, Bacillus licheniformis, lactic acid bacteria and Candida.

[0036] Description: Composite fermentation bacteria can decompose organic matter in water, improve water quality, and inhibit the growth of harmful bacteria in water treatment. Fungi such as Candida can produce flocculants to help aggregate suspended particles in the water and precipitate them, thereby clarifying the water. Microorganisms can change the redox state of water during metabolism, which helps to remove heavy metal ions and other toxic substances in the water. By introducing composite fermentation bacteria, the balance of the water ecosystem can be promoted and aquatic biodiversity can be restored.

[0037] Furthermore, the fermentation humidity is 50-60%.

[0038] Note: Fermentation humidity within the above range helps to create an environment conducive to microbial fermentation, thereby improving fermentation efficiency.

[0039] The beneficial effects of the present invention are:

[0040] The present invention uses calcium ions and organic matter to adjust the medium of the water body to be treated, so that the sample in the water body to be treated can be in a good state. Since calcium ions can coordinate with carbonyl and carboxyl groups in penicillin molecules, the reaction intermediates of hydrolysis are stabilized and the hydrolysis rate of penicillin antibiotics is accelerated. In addition, characteristic functional groups such as amino and thiol groups in biological metabolic organic matter can also be used as strong nucleophilic reagents to promote the rapid hydrolysis of penicillin antibiotics. At the same time, through the specific setting of the method, it is possible to avoid secondary pollution of the water body to be treated by calcium ions and biological organic metabolic media before degradation. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is a flow chart of an embodiment of the present invention. DETAILED DESCRIPTION

[0042] In order to further illustrate the method adopted by the present invention and the effect achieved, the technical solution of the present invention will be clearly and completely described in combination with experiments below.

[0043] Embodiment 1: A method for promoting the degradation of penicillin antibiotics in water, characterized in that it comprises the following steps:

[0044] S1. Water quality testing;

[0045] Detection of penicillin antibiotic concentration and Ca in water 2+ Parameters of concentration, DO and COD;

[0046] S2, medium adjustment;

[0047] Regulation of Ca 2+ Concentration, when Ca in water 2+ The concentration is less than Ca 2+ When the minimum value of the set threshold is reached, calcium-containing substances are added to the water body until Ca 2+ When the concentration reaches the set threshold, 2+ When the concentration is greater than the maximum value of the set threshold, ion exchange resin or lime softening method is used to remove excess Ca 2+ To Ca 2+ The concentration reaches the set threshold;

[0048] The concentration of penicillin antibiotics is 4 mg / L, and the set threshold is 50-100 mg / L;

[0049] When both DO and COD in the water body are within the standard, biological metabolic organic matter is added to the water body until the concentration of biological metabolic organic matter is 10-50 mg / L; the standard of "both DO and COD in the water body are within the standard" is the existing surface water environmental quality standard (the indicators of the three types of water bodies in GB 3838-2002); when both DO and COD in the water body are within the standard, biological metabolic organic matter is not added to the water body;

[0050] The calcium-containing substance is nano-hydroxyapatite doped with calcium ions; the preparation method of the nano-hydroxyapatite doped with calcium ions is:

[0051] S1-1, firstly, CaCl2 and SrCl2 are mixed and dissolved in deionized water according to 9mmol:1mmol:100mL to obtain a first mixed solution;

[0052] S1-2, adding a phosphoric acid solution with a mass concentration of 25% to the first mixed solution while stirring until the pH value reaches 8, to obtain a second mixed solution; the dropping speed is 0.8 mL / s; the stirring speed is 550 rpm;

[0053] S1-3, under continuous stirring, adding ammonia water dropwise to the second mixed solution, adjusting the pH value to 10; then aging the second mixed solution for 14 hours to obtain a suspension; the dropping speed is 0.8 mL / s;

[0054] The aging treatment is to gradually change the temperature of the second mixed solution within a range of 10° C. to 40° C.

[0055] The temperature of the second mixed liquid is gradually changed within the range of 10°C to 40°C: after the temperature of the second mixed liquid is reduced to 10°C, it is heated to 40°C after 1.5 hours, then maintained for 10 minutes, and then cooled to 10°C for 1.5 hours, and the temperature is repeatedly increased and decreased until the treatment is completed.

[0056] S1-4, centrifuging the suspension to obtain a supernatant and a precipitate, removing the supernatant, washing the precipitate with deionized water, and drying the washed precipitate to obtain a dried powder;

[0057] S1-5, calcining the dried powder at 450° C. for 2.5 h to obtain calcium ion-doped nano-hydroxyapatite;

[0058] The preparation method of the biological metabolic organic matter is:

[0059] First, the corn stalks were cut into small pieces of 4 cm; and softened by soaking in water for 12 hours to obtain softened stalks;

[0060] Then, the softened straw is mixed with a composite fermentation agent, wherein the inoculation amount of the composite fermentation agent is 3% of the weight of the straw; and molasses accounting for 8% of the weight of the straw is added;

[0061] The inoculated softened straw is then piled into compost, fermented at 35°C, the pH is adjusted to 6.5, and fermented for 5 weeks, with the pile turned every week; after the fermentation is completed, biological metabolic organic matter is obtained.

[0062] The composite fermentation agent is obtained by mixing Bacillus subtilis, Bacillus licheniformis, lactic acid bacteria and Candida in equal proportions; the fermentation humidity is 55%;

[0063] S3, catalytic degradation;

[0064] 0.5 g / L of photocatalytic material was dispersed in the water; then the pH was adjusted to 7.0, the water temperature was controlled at 20°C, and stirred at a stirring speed of 60 rpm to carry out the hydrolysis reaction; at the same time, the water was irradiated with ultraviolet light at an intensity of 15 mW / cm 2 , irradiation time is 3h;

[0065] S4, precipitation reaction;

[0066] Add 12% of the volume fraction of cells with a density of 1×10 6cells / mL of Spirulina: then by adding NaHCO3, the CO2 concentration in the water is maintained at 6mM; then the pH value is adjusted to 8.8, stirring is started and then 6% 10mg / L polyacrylamide is added as a flocculant, the stirring speed is 120rpm, the stirring time is 35min, and after precipitation for 1h, solid-liquid separation is performed, that is, degradation is completed, and degraded water is obtained.

[0067] Example 2: This example is different from Example 1 in that the concentration of the penicillin antibiotics is 5 mg / L.

[0068] Example 3: This example is different from Example 1 in that the concentration of the penicillin antibiotics is 2 mg / L.

[0069] Example 4: This example is different from Example 1 in that biological metabolizable organic matter is added to the water body until the concentration of biological metabolizable organic matter is 10 mg / L.

[0070] Example 5: This example is different from Example 1 in that biological metabolizable organic matter is added to the water body until the concentration of biological metabolizable organic matter is 50 mg / L.

[0071] Example 6: The difference between this example and Example 1 is that in the S3 catalytic degradation, 1 g / L of photocatalytic material is dispersed in the water body; then the pH is adjusted to 6.5, the water temperature is controlled at 15°C, and stirring is performed at a stirring speed of 80 rpm to carry out a hydrolysis reaction.

[0072] Example 7: The difference between this example and Example 1 is that in the S3 catalytic degradation, 0.1 g / L of photocatalytic material is dispersed in the water body; then the pH is adjusted to 7.5, the water temperature is controlled at 25°C, and stirring is performed at a stirring speed of 40 rpm to carry out a hydrolysis reaction.

[0073] Example 8: This example is different from Example 1 in that, during the catalytic degradation of S3, an ultraviolet lamp is used to irradiate the water body, and the illumination intensity is 10 mW / cm 2 , the irradiation time is 4h.

[0074] Example 9: This example is different from Example 1 in that, during the catalytic degradation of S3, an ultraviolet lamp is used to irradiate the water body, and the illumination intensity is 20 mW / cm 2 , the irradiation time is 2h.

[0075] Example 10: This example is different from Example 1 in that, in the S4 precipitation reaction, 10% of the volume fraction of cells with a density of 1×10 6cells / mL of Spirulina: then CO2 concentration in the water is maintained at 10mM by introducing CO2 gas; then the pH value is adjusted to 8.5.

[0076] Example 11: This example is different from Example 1 in that, in the S4 precipitation reaction, 15% of the volume fraction of cells with a density of 1×10 6 cells / mL of Spirulina: then CO2 concentration in the water was maintained at 5mM by introducing CO2 gas; then the pH value was adjusted to 9.0.

[0077] Example 12: This example is different from Example 1 in that, in the S4 precipitation reaction, stirring is turned on and then polyacrylamide with a volume fraction of 5% 10 mg / L is added as a flocculant, the stirring speed is 100 rpm, and the stirring time is 30 min.

[0078] Example 13: This example is different from Example 1 in that, in the S4 precipitation reaction, stirring is turned on and then polyacrylamide with a volume fraction of 7% 10 mg / L is added as a flocculant, the stirring speed is 150 rpm, and the stirring time is 40 min.

[0079] Example 14: This example is different from Example 1 in that the preparation parameters of the calcium ion-doped nanohydroxyapatite are different. S1-1. First, CaCl2 and SrCl2 are mixed and dissolved in deionized water according to 8mmol:1mmol:100mL to obtain a first mixed solution;

[0080] S1-2, adding a phosphoric acid solution with a mass concentration of 20% to the first mixed solution while stirring until the pH value is 7-9 to obtain a second mixed solution; the dropping speed is 0.5 mL / s; the stirring speed is 500 rpm;

[0081] S1-3, under continuous stirring, slowly dropwise adding ammonia water or sodium hydroxide into the second mixed solution to adjust the pH value to 10; then aging the second mixed solution for 12 hours to obtain a suspension;

[0082] The aging treatment is to subject the second mixed solution to a gradient change within a temperature range of 10° C. to 40° C.

[0083] The second mixed liquid is subjected to a gradient change within the range of 10°C to 40°C: after the temperature of the second mixed liquid is lowered to 10°C, it is heated to 40°C after 1 hour, then maintained for 10 minutes, and then cooled to 10°C for 2 hours, and the temperature is repeatedly raised and lowered until the treatment is completed.

[0084] S1-4, centrifuging the suspension to obtain a supernatant and a precipitate, removing the supernatant, washing the precipitate with deionized water, and drying the washed precipitate to obtain a dried powder;

[0085] S1-5, calcining the dried powder at 400° C. for 2 h to obtain calcium ion-doped nano-hydroxyapatite.

[0086] Example 15: This example is different from Example 1 in that the preparation parameters of the calcium ion-doped nano-hydroxyapatite are different. S1-1. First, CaCl2 and SrCl2 are mixed and dissolved in deionized water according to 10mmol:1mmol:100mL to obtain a first mixed solution;

[0087] S1-2, adding a phosphoric acid solution with a mass concentration of 20-30% to the first mixed solution while stirring until the pH value is 7-9 to obtain a second mixed solution; the dropping speed is 1 mL / s; the stirring speed is 600 rpm;

[0088] S1-3, under continuous stirring, slowly dropwise adding ammonia water or sodium hydroxide into the second mixed solution to adjust the pH value to 10; then aging the second mixed solution for 15 hours to obtain a suspension;

[0089] The aging treatment is to subject the second mixed solution to a gradient change within a temperature range of 10° C. to 40° C.

[0090] The second mixed solution is subjected to a gradient change within the range of 10°C to 40°C: the temperature of the second mixed solution is lowered to 10°C, then raised to 40°C after 2 hours, then maintained for 10 minutes, and then lowered to 10°C for 1 hour, and the temperature is repeatedly raised and lowered until the treatment is completed;

[0091] S1-4, centrifuging the suspension to obtain a supernatant and a precipitate, removing the supernatant, washing the precipitate with deionized water, and drying the washed precipitate to obtain a dried powder;

[0092] S1-5, calcining the dried powder at 500° C. for 3 h to obtain calcium ion-doped nano-hydroxyapatite.

[0093] Example 16: This example differs from Example 1 in that the preparation parameters of the bio-metabolism organic matter are different. First, the corn stalks are cut into small segments of 2 cm; they are softened by steam or water immersion to obtain softened stalks; the softened stalks are then mixed with a composite fermentation bacterial agent in an inoculation amount of 1% of the weight of the stalks; molasses accounting for 5% of the weight of the stalks is added; the inoculated softened stalks are then piled into compost and fermented at 30°C, the pH is adjusted to 6.0, and the fermentation is carried out for 4 weeks, with the compost being turned over every week; after the fermentation is completed, bio-metabolism organic matter is obtained; the fermentation humidity is 50%.

[0094] Example 17: This example differs from Example 1 in that the preparation parameters of the bio-metabolism organic matter are different. First, the corn stalks are cut into small sections of 5 cm; they are softened by steam or water immersion to obtain softened stalks; the softened stalks are then mixed with a composite fermentation bacterial agent in an inoculation amount of 5% of the weight of the stalks; molasses accounting for 10% of the weight of the stalks is added; the inoculated softened stalks are then piled into compost and fermented at 40°C, the pH is adjusted to 7.5, and the fermentation is carried out for 6 weeks, with the pile being turned over every week; after the fermentation is completed, bio-metabolism organic matter is obtained; the fermentation humidity is 60%.

[0095] Example 18: This example is different from Example 1 in that the composite fermentation agent is obtained by mixing Bacillus subtilis and Bacillus licheniformis in equal proportions.

[0096] Example 19: This example is different from Example 1 in that, in the preparation method of biological metabolic organic matter described in S1-5, steam is used for softening, and the steaming time is 4 hours to obtain softened straw.

[0097] Experimental Example: The description of this experimental example is based on the scheme described in Example 1, and is intended to illustrate the practical application effect of the present invention.

[0098] Experimental Example: 1. The methods of Examples 1 to 17 were respectively used to degrade penicillin G in water; the degradation test results are as follows:

[0099] 1. To explore the effects of different treatment methods on the degradation performance of penicillin G;

[0100] Comparative Example 1: The difference from Example 1 is that step S2 is not performed, and steps S3 and S4 are directly performed on the water body.

[0101] Comparative Example 2: The difference from Example 1 is that the threshold is set equal to the concentration of penicillin antibiotics;

[0102] Comparative Example 3: The difference from Example 1 is that the calcium-containing substance is calcium chloride;

[0103] Comparative Example 4: The difference from Example 1 is that no aging treatment is performed;

[0104] Comparative Example 5: The difference from Example 1 is that the treatment of S1-5 is not performed.

[0105] Example 1 and Comparative Examples 1 to 5 were compared, as shown in Table 1;

[0106] Table 1 Degradation experimental results of penicillin G under different treatment methods

[0107]

[0108]

[0109] As can be seen from Table 1, by comparing Example 1 with Comparative Example 1, it can be seen that the degradation effect in Example 1 is better. In contrast, in Comparative Example 1, calcium ions and biological metabolic organic matter are not used to adjust the water environment to promote the degradation process of penicillin antibiotics. Since calcium ions can coordinate with the carbonyl and carboxyl groups in the penicillin molecules to accelerate the hydrolysis rate of penicillin antibiotics, and characteristic functional groups such as amino and thiol in the biological metabolic organic matter can also act as strong nucleophiles to promote the rapid hydrolysis of penicillin antibiotics, Example 1 has this design and therefore has a good degradation effect.

[0110] By comparing Example 1 with Comparative Example 2, it can be seen that compared with setting the threshold of calcium ions to be the same as the concentration of penicillin antibiotics in Comparative Example 2, the corresponding ratio of calcium ions to penicillin antibiotic concentrations in Example 1 is more suitable for the degradation process of antibiotics. This may be because, although calcium ions have a promoting effect on the degradation of antibiotics, when the antibiotic concentration is too high or the calcium ion concentration is too low, calcium ions cannot provide a good environment that promotes antibiotic hydrolysis.

[0111] By comparing Example 1 with Comparative Example 3, it can be seen that the calcium ion used in Comparative Example 3 is calcium chloride. Compared with calcium chloride, the dissolution equilibrium of calcium ion-doped nanohydroxyapatite in water will lead to the gradual release of calcium ions, and the calcium ions on the surface of nanohydroxyapatite can be exchanged with other ions in water, thereby being released into the water body; and the calcium ion-doped nanohydroxyapatite has good biocompatibility, has little effect on organisms in the water body, and can continuously and stably release calcium ions, maintain the calcium ion concentration of the water body, and promote the degradation process.

[0112] By comparing Example 1 with Comparative Example 4, it can be seen that after no aging treatment is performed in Comparative Example 4, the degradation efficiency of penicillin antibiotics is reduced. This may be because the aging treatment and the setting of the temperature gradient in Example 1 can make the crystals in the system grow rapidly and form a specific state to facilitate the subsequent degradation process.

[0113] By comparing Example 1 with Comparative Example 5, it can be found that in Comparative Example 5, no heat treatment is performed, and a more optimized surface structure cannot be generated, so that the surface of the calcium ion-doped nanohydroxyapatite cannot better aggregate heavy metal ions, and without heat treatment, its own crystallinity and stability cannot be improved, thereby affecting the use process.

[0114] 2. Explore the effects of different parameters on the degradation performance of penicillin G;

[0115] Examples 1 to 17 were compared, as shown in Table 1;

[0116] Table 2 Degradation test results of penicillin G under different parameters

[0117] parameter Degradation rate % Example 1 99 Example 2 97 Example 3 98 Example 4 96 Example 5 97 Example 6 95 Example 7 96 Example 8 96 Example 9 95 Example 10 97 Embodiment 11 96 Example 12 95 Example 13 96 Embodiment 14 96 Embodiment 15 97 Example 16 97 Embodiment 17 95

[0118] By comparing Example 1, Example 2 and Example 3, it can be found that the ratio of the concentration of penicillin antibiotics in Example 1 to the calcium ion setting threshold is more preferred; by comparing Example 1, Example 4 and Example 5, it can be found that the concentration of biological metabolic organic matter added to the water body in Example 1 is more preferred, which may be because adding too much will cause linear pollution of the water body, and too little will not achieve a good effect; by comparing Example 1, Example 6 and Example 7, it can be found that the hydrolysis conditions in the catalytic degradation of S3 in Example 1 are better, indicating that different hydrolysis parameters have a certain impact on the degradation of penicillin in the water body, among which the hydrolysis conditions of Example 1 are preferred; by comparing Example 1, Example 8 and Example 7, it can be found that the hydrolysis conditions in the catalytic degradation of S3 in Example 1 are better, indicating that different hydrolysis parameters have a certain impact on the degradation of penicillin in the water body, among which the hydrolysis conditions of Example 1 are preferred; Example 9, it can be found that the illumination conditions of Example 1 are more preferred, which may be because light catalyzes the degradation of penicillin in the water, thereby accelerating the degradation process, wherein the photocatalytic parameters have an impact on the degradation of penicillin G, and the photocatalytic parameters are preferably Example 1; by comparing Example 1, Example 10 and Example 11, it can be found that the parameters of the precipitation treatment in Example 1 are optimal, and Spirulina combined with carbon dioxide can utilize the adsorption capacity of the Spirulina cell surface to adsorb suspended matter and colloidal substances in the water, which is helpful to remove suspended matter and sediment in the water; through the adsorption and precipitation effect of Spirulina, the concentration and turbidity of suspended matter in the water can be reduced, and the transparency of the water can be improved. In addition, Spirulina can absorb and utilize nutrients such as nitrogen and phosphorus in the water during its growth, which helps to reduce the risk of eutrophication of the water. In the system of Spirulina combined with carbon dioxide, the introduction of carbon dioxide not only promotes the growth and degradation ability of Spirulina, but also may affect the formation of sediments by changing the water environment. This synergistic effect helps to remove sediments in the water more efficiently. By comparing Example 1, Example 12 and Example 13, it can be found that the precipitation stirring parameters of Example 1 are more preferred. By comparing Example 1, Example 14 and Example 15, it can be found that the preparation parameters of calcium ion-doped nano-hydroxyapatite in Example 1 are more preferred. By comparing Example 1, Example 16 and Example 17, it can be found that the preparation parameters of biological metabolic organic matter in Example 1 are more preferred.

Claims

1. A method for promoting the degradation of penicillin antibiotics in water, characterized in that: The following steps are involved: S1. Water quality testing; Detection of penicillin antibiotic concentration and Ca in water 2+ Parameters of concentration, DO and COD; S2, medium adjustment; Regulation of Ca 2+ Concentration, when Ca in water 2+ The concentration is less than Ca 2+ When the minimum value of the set threshold is reached, calcium-containing substances are added to the water body until Ca 2+ When the concentration reaches the set threshold, 2+ When the concentration is greater than the maximum value of the set threshold, ion exchange resin or lime softening method is used to remove excess Ca 2+ To Ca 2+ The concentration reaches the set threshold; When the DO and COD in the water body are not over the limit, add biological metabolizable organic matter to the water body until the concentration of biological metabolizable organic matter is 10-50 mg / L; S3, catalytic degradation; Add photocatalytic material to water at a concentration of 0.1-1 g / L and disperse; then adjust the pH to 6.5-7.5, control the water temperature at 15-25°C, and stir at a speed of 40-80 rpm to perform a hydrolysis reaction; at the same time, irradiate the water with ultraviolet light at an intensity of 10-20 mW / cm 2 , irradiation time is 2 to 4 hours; S4, precipitation reaction; Add 10-15% of the volume fraction of cells to the water body with a density of 1×10 6 cells / mL of Spirulina: then maintain the CO2 concentration in the water at 5-10 mM by adding NaHCO3 or passing CO2 gas; then adjust the pH value to 8.5-9.0, start stirring and then add 10 mg / L polyacrylamide with a volume fraction of 5-7% as a flocculant, the stirring speed is 100-150 rpm, the stirring time is 30-40 min, and then solid-liquid separation is carried out after precipitation for 1 hour, and the degradation is completed.

2. A method for promoting the degradation of penicillin antibiotics in water according to claim 1, characterized in that: The set threshold is 50-100 mg / L.

3. A method for promoting the degradation of penicillin antibiotics in water according to claim 1, characterized in that: The standard that both DO and COD in the water body do not exceed the standard is the existing surface water environmental quality standard.

4. A method for promoting the degradation of penicillin antibiotics in water according to claim 1, characterized in that: The calcium-containing substance is calcium ion-doped nano-hydroxyapatite; the preparation method of the calcium ion-doped nano-hydroxyapatite is: S1-1, firstly, CaCl2 and SrCl2 are mixed and dissolved in deionized water according to 8-10 mmol: 1 mmol: 100 mL to obtain a first mixed solution; S1-2, adding a phosphoric acid solution with a mass concentration of 20-30% to the first mixed solution, stirring at the same time, until the pH value is 7-9, to obtain a second mixed solution; wherein the dropping speed is 0.5-1 mL / s; the stirring speed is 500-600 rpm; S1-3, under continuous stirring, adding ammonia water or sodium hydroxide dropwise to the second mixed solution to adjust the pH value to 10; then aging the second mixed solution for 12 to 15 hours to obtain a suspension; S1-4, centrifuging the suspension to obtain a supernatant and a precipitate, removing the supernatant, washing the precipitate with deionized water, and drying the washed precipitate to obtain a dried powder; S1-5, calcining the dried powder at 400-500° C. for 2-3 hours to obtain calcium ion-doped nano-hydroxyapatite.

5. A method for promoting the degradation of penicillins in water as claimed in claim 4, characterized in that: The aging treatment is to gradually change the temperature of the second mixed solution within a range of 10° C. to 40° C.

6. A method for promoting the degradation of penicillins in water as claimed in claim 5, characterized in that: The temperature of the second mixed liquid is gradually changed within 10°C to 40°C: after the temperature of the second mixed liquid is reduced to 10°C, it is heated to 40°C after 1 to 2 hours, then maintained for 10 minutes, and then cooled to 10°C for 1 to 2 hours, and the temperature is repeatedly increased and decreased until the treatment is completed.

7. A method for promoting the degradation of penicillin antibiotics in water according to claim 1, characterized in that: The preparation method of the biological metabolic organic matter is: First, the corn stalks are cut into small segments of 2-5 cm; they are softened by steam or water soaking to obtain softened stalks; Then, the softened straw is mixed with a composite fermentation agent, wherein the inoculation amount of the composite fermentation agent is 1 to 5% of the weight of the straw; and molasses accounting for 5 to 10% of the weight of the straw is added; The inoculated softened straw is then piled into compost, fermented at 30-40°C, the pH is adjusted to 6.0-7.5, and fermented for 4-6 weeks, with the pile turned every week; after the fermentation is completed, biological metabolic organic matter is obtained.

8. A method for promoting the degradation of penicillins in water as claimed in claim 7, characterized in that: The composite fermentation bacterial agent comprises two or more of Bacillus subtilis, Bacillus licheniformis, lactic acid bacteria and Candida.

9. A method for promoting the degradation of penicillins in water as claimed in claim 7, characterized in that: The fermentation humidity is 50-60%.

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