Background
China is a large world for producing and using antibiotics, and more than 300 enterprises produce antibiotics in total, so that 70% of varieties are covered, and the total yield accounts for nearly 80% of the world yield. The production of antibiotic raw material medicines can be roughly divided into two types of fermentation pharmacy and chemical synthesis pharmacy. The fermented antibiotic medicine is produced by a fermentation method, and antibiotic raw material medicines are produced through the processes of separation, purification, refining and the like, wherein each year produces about 200 million tons of antibiotic residues, the average mass content of residual antibiotic and other medicine components is generally more than one thousandth, and if the safe treatment cannot be carried out, the residual medicine components can be transferred and accumulated through an ecological environment system, so that the environment where the human lives is finally damaged, and the human health is seriously threatened.
The key technology of harmless treatment of antibiotic residues is always a major environmental protection problem to be solved in the domestic pharmaceutical industry. Antibiotic residues are used as hazardous waste and need to be disposed or treated. At present, incineration and landfill are mainly used as harmless disposal methods. Wherein, the incineration method is adopted for disposal, so that a first-grade carcinogenic substance dioxin, nitrogen oxides, sulfur dioxide and other harmful gases can be generated, and if the tail gas is not properly treated, secondary harm can be generated; the landfill method is adopted for disposal, so that serious secondary pollution can be caused by organic matter fermentation, and a large amount of valuable land resources are wasted. Therefore, these methods of harmless disposal have drawbacks and the amount of the mushroom dregs to be treated is very limited.
Because the antibiotic residues contain a large amount of organic substances such as crude protein, saccharides, nucleic acids, microbial metabolic intermediates and the like, and contain a large amount of beneficial nutrient elements such as nitrogen, phosphorus, potassium, calcium, magnesium, sulfur and the like, the antibiotic residues have the condition of further comprehensive utilization after harmless treatment to remove harmful components (such as residual antibiotic components) in the antibiotic residues.
Solid products after harmless treatment are taken as raw materials, and can be further processed through a series of treatments to produce soil conditioners for improving the physical and chemical properties of soil, organic and inorganic fertilizers for fertilizing soil fertility, and products such as crude plant protein or amino acid with wide application, so that the added value and the economic benefit in the processes of treating and comprehensively utilizing the mushroom dregs are greatly improved, and the problems of ecological environment safety and precious biomass resource waste are solved.
The existing antibiotic bacterium residues are subjected to harmless treatment mainly by methods such as a biological fermentation degradation method and plasma irradiation.
Chinese patent CN109439693A discloses an anaerobic digestion treatment method of antibiotic fermentation residues, which comprehensively utilizes the generated biogas; chinese patent CN108707559A discloses a tetracycline antibiotic degradation Arthrobacter Arthrobacter sp, which can be used for fermenting and degrading tetracycline antibiotic bacterial residues. However, these methods mainly degrade antibiotics in the mushroom dregs by microorganisms, require a long time and a special fermentation field, and are affected and restricted by environmental temperature and the like.
Chinese patent CN108500034A discloses a treatment process for treating antibiotic residues by plasma irradiation, which adopts electron beams to perform irradiation treatment on antibiotic residues, wherein the electron beams directly act on antibiotic molecules and/or antibiotic genes to destroy the structure of the antibiotic molecules and/or antibiotic genes, and uses free particles to destroy the structure of the antibiotic and antibiotic resistance genes, and simultaneously achieves the purposes of sterilization, disinfection, deodorization and floc breaking, but the treatment process needs high-energy irradiation equipment and larger energy consumption, and has the phenomenon of nondifferential degradation of organic matters.
Disclosure of Invention
The invention aims to provide a method for removing residual antibiotics in antibiotic residue slurry, which can quickly and efficiently degrade antibiotics and other medicinal components in the antibiotic residue and the slurry to be below safe indexes by adopting a physical and chemical integrated treatment and comprehensive utilization technology, and has simple and convenient operation process steps, and is economical and practical.
The purpose of the invention can be realized by the following technical scheme:
a method for removing residual antibiotics from antibiotic residue slurry, the method comprising the steps of:
1) pretreatment: adding an acidic activating agent into the antibiotic mushroom residue slurry, and mixing to obtain activated mushroom residue slurry;
2) oxidative degradation: adding an oxidant into the activated mushroom dreg slurry, and carrying out oxidative degradation to obtain degraded mushroom dreg slurry;
3) and (3) inactivating bacteria: sterilizing the degraded mushroom residue slurry to obtain sterilized mushroom residue slurry;
4) neutralizing: adding an alkaline substance into the sterilized mushroom dreg slurry to obtain neutralized mushroom dreg slurry;
5) and (3) post-treatment: and filtering and drying the neutralized mushroom dreg slurry to obtain a treated product.
Further, the antibiotic mushroom dreg slurry is a mixture of mushroom dreg and slurry which contain residual antibiotic and are generated in the antibiotic production process. In the production process of antibiotics, solid-liquid separation is carried out for multiple times to extract effective medicinal components, so as to obtain solid components and liquid components which become bacterial residues and serous fluid respectively. The antibiotics mainly comprise antibiotics with structures of beta-lactams, aminoglycosides, macrolides, polypeptides, tetracyclines, antifungal agents and the like.
Furthermore, the solid content of the antibiotic dreg serous fluid is 18 to 45 percent.
Further, in step 1), the acidic activator comprises one or more of potassium bisulfate, phosphorus pentoxide, nitric acid or citric acid. The purpose of adding the acidic activator is: providing H required in oxidation reaction system+. Adding water for size mixing, or adding the liquid product obtained by filtering and separating in the step 5) as the circulating mother liquor.
Further, in the step 1), the solid content of the activated mushroom dreg slurry is 6-20%, and the pH value is 2.1-5. The solid content is controlled within the range, so as to ensure solid-liquid two-state substances in a heterogeneous reaction systemThe antibacterial agent has good fluidity and dispersibility, and ensures that residual antibiotics in the system are degraded quickly and efficiently; the pH value is controlled within the range, mainly ensuring H in the system+The most suitable range is maintained.
Further, in step 2), the oxidant comprises one or more of sodium nitrite, chlorine dioxide, calcium peroxide, sodium percarbonate or permanganate; the mass ratio of the oxidant to the antibiotic bacteria dreg serous fluid is (0.01-0.1): 1.
Further, a catalyst is added in the oxidative degradation process, and the catalyst comprises one or two of ferrous acetate or manganese acetate; the mass ratio of the catalyst to the oxidant is (0.001-0.03): 1.
Further, in the step 2), the temperature is 10-100 ℃ and the time is 1-10 hours in the oxidative degradation process; in the step 3), the temperature is 120-160 ℃, the pressure is 0.1-0.6Mpa, and the time is 5-30 minutes in the sterilization treatment process. The sterilization treatment is to kill the residual microbial activity in the bacterial dregs. During the sterilization treatment, physicochemical sterilization is realized through higher temperature (physical sterilization) and chemical oxidation (chemical sterilization combined killing and destroying the activity of microorganisms).
Further, in step 4), the alkaline substance comprises one or more of sodium hydroxide, calcium hydroxide or ammonia water, and the pH value of the neutralized mushroom dreg slurry is 5.5-7. The purpose of neutralization is: ensures that the products after innocent treatment meet the control index requirements of pH value in the organic fertilizer, and can be comprehensively utilized.
Further, in the step 5), the filtration is centrifugal filtration or filter pressing, and the drying is low-temperature drying, high-temperature drying or vacuum drying. The treated product obtained after drying is a solid product with a water content of 10 wt% to 50 wt%.
In the antibiotic dreg slurry, the content of antibiotic residues is usually in the range of hundreds to thousands of mg/kg, and the content of antibiotic drug residues is very high. After the treatment of the invention, the antibiotic content in the solid product is less than 10mg/kg, and the antibiotic content in the liquid product and the waste water is less than 1 mg/kg.
After the antibiotics remained in the antibiotic mushroom dreg slurry are removed, organic nutrient substances such as protein, amino acid, nucleic acid, saccharides and the like in the mushroom dreg beneficial to the growth of plants and crops are reserved, namely, the removal of the antibiotics in the mushroom dreg is preferentially selective, and the total mass loss rate (measured by drying) of the processed mushroom dreg is less than 20%.
Compared with the prior art, the invention has the following characteristics:
1) the invention adopts an oxidation treatment and sterilization integrated technology, can simultaneously remove antibiotic residues and residual antibiotics in the serous fluid, has high removal rate, does not generate secondary pollution products, belongs to cleaning treatment, and has low comprehensive treatment cost of the residues, rapid and environment-friendly treatment process, mild process conditions, less consumption of used activating agent, catalyst and oxidant, simple operation process and strong engineering applicability;
2) the product after the harmless treatment is a solid product with the water content of 10-50 wt%, is safe and nontoxic, has removed harmful substances, retains a large amount of nutrient substances required by the growth of plants and crops, has an organic matter content of 50-80% and a total content of nitrogen, phosphorus and potassium of 5-8%, can be directly used for preparing a soil conditioner or an organic fertilizer, can also be used as a raw material of products such as a soil conditioner, an organic fertilizer, an organic-inorganic fertilizer, a compound fertilizer and the like, can further extract crude protein or various amino acid products, realizes the comprehensive recycling, and has more obvious technical and economic properties.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
the bacteria residue slurry to be treated is 500g of the cephalosporin bacteria residue slurry mixture, the solid content is 20 percent, and the content of cephalosporin C in the bacteria residue slurry is 2500mg/kg (dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 15%, and adjusting pH to 3 with potassium bisulfate.
Step (2): at the temperature of 90 ℃, 25g of calcium peroxide serving as an oxidant and 0.25g of ferrous acetate serving as a catalyst are added, and the mixture is stirred and reacted for 2 hours.
And (3): after the reaction is finished, steam sterilization is carried out for 10 minutes under the conditions of 130 ℃ and 0.3 Mpa.
And (4): the pH of the system was then adjusted to 5.8 with sodium hydroxide.
And (5): the mixture was filtered under pressure and dried at high temperature to obtain 105g (84 g on a dry basis) of a product having a water content of 20%.
In the solid product after detection treatment, the residue of cephalosporin C is 0.8mg/kg, the content of organic matter (dry basis) is 55%, and the total content of nitrogen, phosphorus and potassium (dry basis) is 5.8%.
The residual amount of cephalosporin C in the wastewater (slurry) was 0.05 mg/kg.
Example 2:
the bacterial dreg slurry to be treated is 200g of penicillin bacterial dreg slurry mixture, the solid content is 20%, and the penicillin content in the bacterial dreg slurry is 1200mg/kg (dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 10%, and adjusting the pH of the system to 2.1 by using phosphorus pentoxide.
Step (2): at the temperature of 50 ℃, 2.5g of potassium permanganate serving as an oxidant is added, and the mixture is stirred and reacted for 8 hours.
And (3): after the reaction is finished, steam sterilization is carried out for 20 minutes under the conditions of 120 ℃ and 0.1 Mpa.
And (4): the pH of the system was then adjusted to 6.8 with potassium hydroxide.
And (5): drying by filtration and evaporation gave 48g (36 g on a dry basis) of product with 25% water content.
In the solid product after detection treatment, the residual amount of penicillin is 0.5mg/kg, the content of organic matters (calculated on a dry basis) is 48.5%, and the total content of nitrogen, phosphorus and potassium (calculated on a dry basis) is 5.1%. The residual amount of penicillin in the waste water (slurry) is less than 0.02 mg/kg.
Example 3:
the mushroom dreg slurry to be treated is 2000g of apramycin mushroom dreg slurry mixture, the solid content is 45%, and the apramycin content in the mushroom dreg slurry is 2800mg/kg (on a dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 20%, and adjusting the pH value of the system to 4 by using nitric acid.
Step (2): 20g of oxidizing agent chlorine dioxide is added at 25 ℃, and the mixture is stirred and reacted for 10 hours.
And (3): after the reaction is finished, steam sterilization is carried out for 25 minutes under the conditions of 155 ℃ and 0.5 Mpa.
And (4): the pH of the system was then adjusted to 6 with sodium hydroxide.
And (5): by filtration and drying at low temperature, 465g (335 g on a dry basis) of the product having a water content of 28% was obtained.
In the solid product after detection treatment, the residual quantity of apramycin is 2.3mg/kg, the content of organic matters (calculated on a dry basis) is 51.5 percent, and the total content of nitrogen, phosphorus and potassium (calculated on a dry basis) is 4.8 percent.
The residual quantity of apramycin in the wastewater (slurry) is 0.06 mg/kg.
Example 4:
the mushroom dreg slurry to be treated is 100g of the mixture of lincomycin mushroom dreg slurry, the solid content is 43 percent, and the lincomycin content in the mushroom dreg slurry is 3720mg/kg (calculated on a dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 10%, and adjusting pH of the system to 4.5 with citric acid.
Step (2): at the temperature of 100 ℃, 2g of sodium percarbonate serving as an oxidant and 0.02g of manganese acetate serving as a catalyst are added, and the mixture is stirred and reacted for 1 hour.
And (3): after the reaction is finished, steam sterilization is carried out for 30 minutes under the conditions of 130 ℃ and 0.3 Mpa.
And (4): the pH of the system was then adjusted to 6.5 with aqueous ammonia.
And (5): the reaction mixture was filtered under pressure and dried at low temperature to obtain 19g (16.1 g on a dry basis) of a product having a water content of 15%.
The solid product after detection treatment has lincomycin residue of 0.9mg/kg, organic matter content (dry basis) of 52.8%, and total content of nitrogen, phosphorus and potassium (dry basis) of 5.5%.
The residual quantity of lincomycin in the waste water (slurry) is 0.02 mg/kg.
Example 5:
the bacteria dreg slurry to be treated is 500g of maduramicin bacteria dreg slurry mixture, the solid content is 18%, and the maduramicin bacteria dreg slurry content is 1900mg/kg (dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 6%, and adjusting pH to 5 with potassium bisulfate.
Step (2): 12.5g of calcium peroxide as an oxidant is added at the temperature of 80 ℃, and the mixture is stirred and reacted for 3 hours.
And (3): after the reaction is finished, steam sterilization is carried out for 10 minutes under the conditions of 140 ℃ and 0.4 Mpa.
And (4): the pH of the system was then adjusted to 5.7 with sodium hydroxide.
And (5): filtration under pressure and evaporation to dryness gave 85g (76.5 g on a dry basis) of the product having a water content of 10%.
In the solid product after detection treatment, the residual amount of maduramicin mushroom dregs is 1.2mg/kg, the content of organic matters (calculated on a dry basis) is 46 percent, and the total content of nitrogen, phosphorus and potassium (calculated on a dry basis) is 5.7 percent. The residual quantity of maduramicin bacterial dregs in the waste water (slurry) is 0.07 mg/kg.
Example 6:
the mushroom dreg slurry to be treated is 1000g of the mixture of the aureomycin mushroom dreg slurry, the solid content is 41 percent, and the aureomycin content in the mushroom dreg slurry is 3200mg/kg (calculated on a dry basis). The treatment process comprises the following steps:
step (1): adding water to form slurry with solid content of 15%, and adjusting the pH value of the system to 2.5 by using nitric acid.
Step (2): 20g of sodium percarbonate as an oxidant and 0.6g of ferrous acetate as a catalyst are added at the temperature of 70 ℃, and the mixture is stirred and reacted for 5 hours.
And (3): after the reaction is finished, steam sterilization is carried out for 30 minutes at 135 ℃ and 0.35 Mpa.
And (4): the pH of the system was then adjusted to 6.6 with aqueous ammonia.
And (5): filtration and drying at high temperature gave 215g (172 g on a dry basis) of the product having a water content of 20%.
In the solid product after detection treatment, the residual quantity of the aureomycin is 0.65mg/kg, the content of organic matters (calculated on a dry basis) is 53 percent, and the total content of nitrogen, phosphorus and potassium (calculated on a dry basis) is 6.5 percent. The residual quantity of the aureomycin in the waste water (slurry) is 0.12 mg/kg.
Example 7:
a method for removing residual antibiotics in antibiotic dreg slurry comprises the following steps:
1) pretreatment: adding an acidic activating agent into the antibiotic mushroom residue slurry, and mixing to obtain activated mushroom residue slurry;
2) oxidative degradation: adding an oxidant into the activated mushroom dreg slurry, and carrying out oxidative degradation to obtain degraded mushroom dreg slurry;
3) and (3) inactivating bacteria: sterilizing the degraded mushroom residue slurry to obtain sterilized mushroom residue slurry;
4) neutralizing: adding an alkaline substance into the sterilized mushroom dreg slurry to obtain neutralized mushroom dreg slurry;
5) and (3) post-treatment: and filtering and drying the neutralized mushroom dreg slurry to obtain a treated product.
The antibiotic bacteria dreg slurry is a mixture of bacteria dreg and slurry which contain residual antibiotic and are generated in the antibiotic production process. The solid content in the antibiotic residue slurry is 18%.
In the step 1), the acidic activating agent is potassium bisulfate. The solid content of the activated mushroom dreg slurry is 6 percent, and the pH value is 2.1.
In the step 2), the oxidant is permanganate; the mass ratio of the oxidant to the antibiotic dreg serous fluid is 0.01: 1. A catalyst is also added in the oxidative degradation process, and the catalyst is ferrous acetate; the mass ratio of the catalyst to the oxidant is 0.03: 1. In the oxidative degradation process, the temperature is 10 ℃, and the time is 10 hours;
in the step 3), the temperature is 120 ℃, the pressure is 0.6Mpa and the time is 5 minutes in the sterilization process.
In the step 4), the alkaline substance is ammonia water, and the pH value of the neutralized mushroom dreg slurry is 5.5.
In the step 5), the filtration is centrifugal filtration, and the drying is low-temperature drying.
Example 8:
a method for removing residual antibiotics in antibiotic dreg slurry comprises the following steps:
1) pretreatment: adding an acidic activating agent into the antibiotic mushroom residue slurry, and mixing to obtain activated mushroom residue slurry;
2) oxidative degradation: adding an oxidant into the activated mushroom dreg slurry, and carrying out oxidative degradation to obtain degraded mushroom dreg slurry;
3) and (3) inactivating bacteria: sterilizing the degraded mushroom residue slurry to obtain sterilized mushroom residue slurry;
4) neutralizing: adding an alkaline substance into the sterilized mushroom dreg slurry to obtain neutralized mushroom dreg slurry;
5) and (3) post-treatment: and filtering and drying the neutralized mushroom dreg slurry to obtain a treated product.
The antibiotic bacteria dreg slurry is a mixture of bacteria dreg and slurry which contain residual antibiotic and are generated in the antibiotic production process. The solid content in the antibiotic residue slurry was 45%.
In the step 1), the acidic activating agent is phosphorus pentoxide. The solid content of the activated mushroom dreg slurry is 20 percent, and the pH value is 5.
In the step 2), the oxidant comprises chlorine dioxide and calcium peroxide; the mass ratio of the oxidant to the antibiotic dreg serous fluid is 0.1: 1. A catalyst is also added in the oxidative degradation process, and the catalyst is manganese acetate; the mass ratio of the catalyst to the oxidant is 0.001: 1. In the oxidative degradation process, the temperature is 100 ℃, and the time is 1 hour;
in the step 3), the temperature is 160 ℃, the pressure is 0.1Mpa and the time is 30 minutes in the sterilization process.
In the step 4), the alkaline substance is calcium hydroxide, and the pH value of the neutralized mushroom dreg slurry is 7.
In the step 5), the filtration is filter pressing, and the drying is high-temperature drying.
Example 9:
a method for removing residual antibiotics in antibiotic dreg slurry comprises the following steps:
1) pretreatment: adding an acidic activating agent into the antibiotic mushroom residue slurry, and mixing to obtain activated mushroom residue slurry;
2) oxidative degradation: adding an oxidant into the activated mushroom dreg slurry, and carrying out oxidative degradation to obtain degraded mushroom dreg slurry;
3) and (3) inactivating bacteria: sterilizing the degraded mushroom residue slurry to obtain sterilized mushroom residue slurry;
4) neutralizing: adding an alkaline substance into the sterilized mushroom dreg slurry to obtain neutralized mushroom dreg slurry;
5) and (3) post-treatment: and filtering and drying the neutralized mushroom dreg slurry to obtain a treated product.
The antibiotic bacteria dreg slurry is a mixture of bacteria dreg and slurry which contain residual antibiotic and are generated in the antibiotic production process. The solid content in the antibiotic residue slurry is 30%.
In the step 1), the acidic activating agent comprises nitric acid and citric acid. The solid content of the activated mushroom dreg slurry is 18 percent, and the pH value is 4.
In the step 2), the oxidant comprises sodium nitrite and sodium percarbonate; the mass ratio of the oxidant to the antibiotic dreg serous fluid is 0.05: 1. A catalyst is also added in the oxidative degradation process, and the catalyst is ferrous acetate; the mass ratio of the catalyst to the oxidant is 0.02: 1. In the oxidative degradation process, the temperature is 55 ℃ and the time is 6 hours;
in the step 3), the temperature is 140 ℃, the pressure is 0.3Mpa and the time is 20 minutes in the sterilization process.
In the step 4), the alkaline substance is sodium hydroxide, and the pH value of the neutralized mushroom dreg slurry is 6.5.
In the step 5), the filtration is centrifugal filtration, and the drying is vacuum drying.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.