CN116213434A - A kind of processing method of erythromycin thiocyanate bacteria residue - Google Patents

Abstract

The invention provides a treatment method for erythromycin thiocyanate bacteria residue, which comprises: A) carrying out electron beam irradiation treatment with erythromycin thiocyanate bacteria residue; B) treating the thiocyanate obtained in step A) The erythromycin residue is inoculated with anaerobic sludge for anaerobic fermentation; C) the fermentation liquid obtained in step C) is subjected to electron beam irradiation advanced treatment, and the obtained fermentation liquid is enriched and concentrated to obtain a biomass carbon source. The treatment method of erythromycin thiocyanate slag provided by the application is combined with electron beam pretreatment and anaerobic fermentation, and electron beam advanced treatment is carried out again, which solves the problem of antibiotic residue and The problem of resistance genes; solved the problem of high dosage of acid, alkali and oxidant in the erythromycin thiocyanate slag treatment process, resulting in high inorganic salt content in the follow-up slag; solved the need to add a large amount of fresh water The problem of dilution and the problem that macromolecular organic substances such as proteins and lipids in mycelia are difficult to be utilized by microorganisms.

Description

A kind of processing method of erythromycin thiocyanate bacteria residue

technical field

The invention relates to the technical field of biohazardous waste treatment, in particular to a treatment method for erythromycin thiocyanate slag.

Background technique

Erythromycin thiocyanate is the thiocyanate of erythromycin, a macrolide antibiotic. Erythromycin thiocyanate is a key intermediate raw material for the synthesis of macrolide antibiotics such as erythromycin, roxithromycin, azithromycin and clarithromycin, and has a high market value. However, erythromycin thiocyanate can only be obtained through microbial fermentation at present, and cannot be artificially synthesized in large quantities in the industry. Erythromycin thiocyanate residue is the residual culture medium produced during the production of antibiotics by microbial fermentation. Generally, 8-10 tons of wet residue can be produced for every ton of antibiotic produced. In 2020, about 220 tons of fermentation antibiotic residue will be produced in my country. tons. If the fresh erythromycin thiocyanate residue is not treated, random stacking will easily produce stench. At the same time, residual antibiotics and resistance genes in the residue will easily pollute soil and water sources, produce super-resistant bacteria, and endanger human health. The "National Hazardous Waste List" promulgated in 2008 and newly revised and implemented in 2016 listed erythromycin thiocyanate residue as hazardous waste.

There are mycelia, microbial metabolites, medium degradation products and residual antibiotics in the erythromycin thiocyanate residue, which contains a large amount of crude protein, crude fiber, amino acids and trace elements, and has high potential utilization value. Under the background of continuous improvement of environmental protection requirements and sustainable development strategy, as the world's largest antibiotic production country, my country has an urgent need for harmless treatment and resource utilization treatment technology, and research efforts on the treatment and utilization technology of erythromycin thiocyanate residue is also increasing.

At present, the treatment process of erythromycin thiocyanate slag includes: mechanical stirring + ultrasonic pretreatment followed by drying; acidic active agent, oxidant and catalyst treatment; high temperature and high pressure pretreatment followed by dry composting; anaerobic digestion after dilution with water. CN101380509 B discloses a method for harmless treatment of macrolide antibiotic slag, the method first adopts three-stage multi-circuit countercurrent mechanical stirring+three-stage multi-circuit drying+microbial agent fermentation, in the method countercurrent mechanical stirring Ultrasonic assistance is required, and the drying process consumes a lot of energy and is prone to odor. After drying, it needs to be adjusted by adding water before fermentation, resulting in high cost and cumbersome process. CN 112408685A discloses a method of adding acidic activators, oxidants and catalysts to degrade thierythromycin, and then adding alkaline agents to neutralize after high temperature and high pressure sterilization. In this method, a large amount of inorganic salts will limit the use and amount of bacteria residue , may induce environmental pollution such as soil salinization, the sterilization stage requires high temperature and high pressure conditions, and the acidic environment has higher requirements for equipment and higher operating costs. Application number: 201310162405.0 discloses a method of degrading erythromycin at a temperature above 160°C, and then drying it to prepare organic fertilizer. This method requires a high temperature and high pressure environment, which requires extremely high energy and equipment, and has great potential safety hazards. The subsequent drying process will also produce peculiar smell and stench; CN104593433B discloses a method and equipment for treating antibiotic residues. In this method, the residues of bacteria are first diluted with clean water, and then anaerobic digestion is performed. The dilution of clean water leads to a large increase in the content of hazardous waste.

Based on the problems existing in the above-mentioned erythromycin thiocyanate slag treatment process, the present invention proposes a technical process route of electron beam irradiation pretreatment + anaerobic hydrolysis acidification + electron beam advanced treatment.

Contents of the invention

The technical problem solved by the present invention is to provide a treatment method for erythromycin thiocyanate residue, which can effectively remove residual antibiotics and resistance genes in the residue of erythromycin thiocyanate.

In view of this, the application provides a kind of treatment method of erythromycin thiocyanate slag, comprising the following steps:

A) the erythromycin thiocyanate slag is subjected to electron beam irradiation;

B) the erythromycin thiocyanate slag that step A) obtains is inoculated with anaerobic sludge and carried out anaerobic fermentation;

C) carrying out the advanced treatment of the fermented liquid obtained in step B) by electron beam irradiation;

D) The fermentation broth obtained in step C) is subjected to centrifugation-membrane filtration enrichment and concentration to obtain a biomass carbon source.

Preferably, in step A), the electron beam accelerator energy of the electron beam irradiation treatment is 1-2 MeV, and the beam current is 30-80 mA.

Preferably, in step A), the absorbed dose of the erythromycin thiocyanate residue is 50-500 kGy.

Preferably, the anaerobic sludge is subjected to electron beam irradiation treatment in advance, and the absorbed dose of the electron beam irradiation advanced treatment is 3-10 kGy.

Preferably, the initial pH of the anaerobic fermentation is 5-7, the temperature is 25-35°C, the inoculation amount of the anaerobic sludge is 2-5% VS (w/v) of the entire fermentation volume, the The solid content rate of the anaerobic fermentation system is 3-6%; the time of the anaerobic fermentation is 5-10 days.

Preferably, in step C), the electron beam accelerator energy of the electron beam irradiation deep treatment is 1-2 MeV, the beam current is 30-80 mA, and the absorbed dose of the electron beam irradiation deep treatment is 30-100 kGy.

Preferably, the TS of the erythromycin thiocyanate residue is 7.21-9.32%, the VS is 5.67-7.30%, the water content is 90.68-92.79%, the pH is 4.98-5.84, and the residual erythromycin residue is mixed with Liquid 108.34～434.79ppm, bacterial residue supernatant 175.69～263.00ppm, bacterial residue sediment 249.20～400.00ppm.

The application provides a treatment method for erythromycin thiocyanate slag, which includes sequential electron beam pretreatment-anaerobic fermentation acid production-electron beam advanced treatment-centrifugation-membrane filtration-biomass carbon source depletion Hazardous technology route. The treatment method of erythromycin thiocyanate slag provided by the application is combined with electron beam pretreatment and anaerobic fermentation, and electron beam advanced treatment is carried out again, which solves the problem of antibiotic residue and The problem of resistance genes; solve the problem of high dosage of acid, alkali and oxidant in the erythromycin thiocyanate slag treatment process, resulting in high inorganic salt content in the follow-up slag; solve the need to add a large amount of fresh water The problem of dilution and the problem that macromolecular organic substances such as proteins and lipids in mycelia are difficult to be utilized by microorganisms.

Furthermore, the treatment method provided by the present application solves the problem of using high-temperature and high-pressure heating equipment, which leads to high requirements for equipment maintenance and operation, and has certain potential safety hazards; it also solves the problems of a large amount of peculiar smell and large energy consumption during the high-temperature drying process.

Description of drawings

Fig. 1 is the process flowchart of the erythromycin thiocyanate bacterial residue provided by the invention;

Fig. 2 is the curve diagram of the changing situation of dissolved organic matter in different fermenting bottle anaerobic process that the embodiment of the present invention 2 provides;

Fig. 3 is a graph showing the variation of erythromycin residues in different fermentation flask anaerobic processes provided by Example 2 of the present invention.

Detailed ways

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention.

In view of the necessity and existing problems of erythromycin thiocyanate slag treatment in the prior art, the application provides a treatment method for erythromycin thiocyanate slag, which is carried out sequentially through electron beam pretreatment- Anaerobic fermentation acid production-electron beam advanced treatment-centrifugal separation-membrane filtration solves the problem of antibiotic residues in fermented erythromycin-like erythromycin residues, especially thioerythromycin residues; solves the problem of existing thiocyanate In the erythromycin residue treatment process, the dosage of acid, alkali and oxidant is large, which leads to the problem that the content of inorganic salt in the follow-up bacteria residue is too high; The problem that macromolecular organic substances such as proteins and lipids are difficult to be utilized by microorganisms. Specifically, the embodiment of the present invention discloses a treatment method for erythromycin thiocyanate slag, comprising the following steps:

A) the erythromycin thiocyanate slag is subjected to electron beam irradiation;

B) the erythromycin thiocyanate slag that step A) obtains is inoculated with anaerobic sludge and carried out anaerobic fermentation;

C) carrying out the advanced treatment of the fermented liquid obtained in step B) by electron beam irradiation;

D) The fermentation broth obtained in step C) is subjected to centrifugation-membrane filtration enrichment and concentration to obtain a biomass carbon source.

The technical process adopted in the present invention: erythromycin thiocyanate bacteria residue-electron beam pretreatment-anaerobic fermentation acid production-electron beam advanced treatment-biomass carbon source harmless technical route, as shown in Figure 1.

In this application, the erythromycin thiocyanate slag is first subjected to electron beam irradiation treatment. The electron beam irradiation is to act on the substance through the electron beam generated by the electron accelerator, which is a unique advanced oxidation-reduction technology. The principle includes the direct radiation of high-energy electron beams and the oxidation-reduction of active particles such as ·OH, O ₂ · ^- , HO ₂ ·, e _aq ^- , ·H when the electron beam excites water molecules (as shown in the following formula); The system will produce chemical effects and biological effects, achieving the effect of removing organic matter and killing microorganisms at the same time.

Compared with traditional advanced oxidation technology, electron beam irradiation has more active particles, more complex oxidation-reduction process, richer reaction effects and more diverse process combinations in the electron beam pollution control system, so it can be more Efficient and low-cost treatment of fermented erythromycin thiocyanate residue.

In the present application, the electron beam irradiation treatment specifically includes: injecting the uniformly mixed erythromycin thiocyanate slag into the electron beam irradiation pretreatment unit through a screw pump, adjusting the energy of the electron beam accelerator to 1-2 MeV, The beam current is 30-80mA, so that the absorbed dose of the fungus residue reaches 50-500kGy; more specifically, the electron beam accelerator energy of the electron beam irradiation treatment is 1.2-1.8MeV, the beam current is 40-50mA, and the absorbed dose 100-200 kGy.

The irradiated bacterial residue is put into the anaerobic fermentation unit and inoculated with anaerobic sludge for anaerobic fermentation; the anaerobic sludge has been irradiated in advance, and the absorbed dose is 3-10kGy, and the treatment is 30-60min to inhibit Methanogens among them. The inoculum ratio of anaerobic sludge is 2 to 5% VS (w/v), the initial pH of anaerobic fermentation is adjusted to 5 to 7 with dilute hydrochloric acid or dilute sodium hydroxide, and the reaction temperature of anaerobic fermentation is controlled to be 25 to 35°C. The solid content is 3% to 6%, and anaerobic fermentation is started to produce acid, and the time of anaerobic fermentation reaction is controlled to be 5 to 10 days; more specifically, the absorbed dose is 5 to 8kGy, and the treatment time is 40 to 60min. The temperature of anaerobic fermentation is 30-35 DEG C, and the time is 5-7 days.

The applicant then injects the fermented liquid after the anaerobic fermentation reaction into the electron beam irradiation reactor for advanced treatment, adjusts the energy of the electron beam accelerator to 1-2 Mev, the beam current to 30-80 mA, and the absorbed dose to 30-100 kGy, more specifically , the energy of the electron beam accelerator is 1.5-2MeV, the beam current is 40-80mA, and the absorbed dose is 50-100kGy. During this process, the degradation of antibiotic residues and resistance genes in the anaerobic fermentation broth after advanced treatment with electron beams can be detected by liquid chromatography-mass spectrometry and fluorescent quantitative PCR technology.

At the end of the application, the anaerobic fermentation liquid after electron beam advanced treatment is subjected to centrifugation-membrane filtration enrichment and concentration to make biomass carbon source, which is used to supplement the carbon source of denitrification reaction in sewage treatment biochemical system.

In order to further understand the present invention, the treatment method of the erythromycin thiocyanate bacterial residue provided by the present invention is described in detail below in conjunction with the examples, and the protection scope of the present invention is not limited by the following examples.

The erythromycin thiocyanate bacterial residue used in the following examples of the present invention is taken from a certain erythromycin thiocyanate fermentation workshop in Xinjiang, and the indicators are as shown in Table 1;

Table 1 basic properties of erythromycin thiocyanate slag used in the present invention

Example 1

Electron beam pretreatment of erythromycin thiocyanate slag: inject the uniformly mixed erythromycin thiocyanate slag into the electron beam irradiation pretreatment unit through a screw pump, adjust the energy of the electron accelerator to 2MeV, and the beam current to 50mA, so that The absorbed dose of fungus residue reaches 200kGy;

Pretreatment of anaerobic inoculated sludge: put anaerobic inoculated sludge into the electron beam irradiation treatment unit, adjust the electron accelerator energy to 2 Mev, beam current 2mA, so that the absorbed dose of anaerobic inoculated sludge reaches 5kGy;

Anaerobic fermentation acid production: the anaerobic inoculated sludge was mixed with the erythromycin thiocyanate residue after electron beam pretreatment, the inoculation ratio of the anaerobic sludge was 3% VS (w/v), and the anaerobic fermentation produced The solid content of the acid system is controlled at 5%, and then the pH is adjusted to 7.0 with dilute hydrochloric acid. After sealing, anaerobic fermentation is carried out to produce acid. The temperature of anaerobic fermentation for acid production is 35°C, and the reaction time is controlled to 7 days;

Advanced treatment of anaerobic fermentation broth: Put the fermentation broth after anaerobic fermentation into the electron beam irradiation reactor for advanced treatment, remove residual antibiotics and resistance genes, adjust the electron accelerator energy to 2 Mev, beam current 50mA, and make the fermentation broth The absorbed dose was 100kGy; the anaerobic fermentation broth was detected by liquid phase mass spectrometry and fluorescent quantitative PCR technology before and after electron beam advanced treatment of antibiotic residues and degradation of resistance genes; the results are shown in Table 2;

Preparation of biomass carbon source from anaerobic fermentation broth: Advanced treatment of anaerobic fermentation broth by electron beams, enrichment and concentration to produce biomass carbon source, which is used to supplement the carbon source of denitrification reaction in sewage treatment biochemical system.

Degradation data table after table 2 erythromycin thiocyanate slag treatment

Example 2

Pretreatment of erythromycin thiocyanate slag: inject the uniformly mixed erythromycin thiocyanate slag into the electron beam irradiation pretreatment unit through a screw pump, adjust the energy of the electron accelerator to 2MeV, and the beam current to 50mA, so that the erythromycin thiocyanate slag The absorbed dose reached 150kGy; untreated erythromycin thiocyanate slag was used as a control;

Pretreatment of anaerobic inoculated sludge: Put the anaerobic inoculated sludge into the electron beam irradiation treatment unit, adjust the energy of the electron accelerator to 2 Mev, and the beam current to 2mA, so that the absorbed dose of the anaerobic inoculated sludge can reach 5kGy; The anaerobic inoculation sludge treated with beam irradiation was used as a control;

Acid production by anaerobic fermentation: the anaerobic inoculation sludge after electron beam irradiation was mixed with erythromycin thiocyanate residue after electron beam pretreatment, and the erythromycin thiocyanate residue without electron beam irradiation pretreatment was mixed. The erythromycin thiocyanate residue without electron beam irradiation pretreatment and the anaerobic inoculation sludge without electron beam irradiation treatment were mixed as control. Mud was mixed as a contrast, the inoculation ratio of anaerobic inoculated sludge anaerobic sludge was 3% VS (w/v), the solid content of anaerobic fermentation acid production system was controlled at 3%, and then the pH was adjusted to 7.0, carry out anaerobic fermentation acid production after airtight, the temperature of anaerobic fermentation acid production is 35 ℃, the reaction time is controlled at 8 days; Figure 3 shows.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. a processing method of erythromycin thiocyanate bacterium residue, comprises the following steps: A) the erythromycin thiocyanate slag is subjected to electron beam irradiation; B) the erythromycin thiocyanate slag that step A) obtains is inoculated with anaerobic sludge and carried out anaerobic fermentation; C) carrying out the advanced treatment of the fermented liquid obtained in step B) by electron beam irradiation; D) The fermentation broth obtained in step C) is subjected to centrifugation-membrane filtration enrichment and concentration to obtain a biomass carbon source. 2 . The treatment method according to claim 1 , characterized in that, in step A), the electron beam accelerator energy of the electron beam irradiation treatment is 1-2 MeV, and the beam current is 30-80 mA. 3. The treatment method according to claim 1, characterized in that, in step A), the absorbed dose of the erythromycin thiocyanate bacterial residue is 50-500 kGy. 4 . The treatment method according to claim 1 , wherein the anaerobic sludge is subjected to electron beam irradiation treatment in advance, and the absorbed dose of the electron beam irradiation advanced treatment is 3-10 kGy. 5. The treatment method according to claim 4, characterized in that, the initial pH of the anaerobic fermentation is 5 to 7, the temperature is 25 to 35°C, and the inoculation amount of the anaerobic sludge is 1/2 of the entire fermentation volume. 2-5% VS (w/v), the solid content rate of the anaerobic fermentation system is 3-6%; the time of the anaerobic fermentation is 5-10 days. 6. The processing method according to claim 1, characterized in that, in step C), the electron beam accelerator energy of the electron beam irradiation depth treatment is 1～2MeV, the beam current is 30～80mA, and the electron beam irradiation The absorbed dose of advanced treatment is 30-100kGy. 7. The treatment method according to claim 1, characterized in that, the TS of the erythromycin thiocyanate residue is 7.21 to 9.32%, the VS is 5.67 to 7.30%, the water content is 90.68 to 92.79%, and the pH It is 4.98～5.84, the residual erythromycin in the bacterial residue mixture is 108.34～434.79ppm, the bacterial residue supernatant is 175.69～263.00ppm, and the bacterial residue precipitate is 249.20～400.00ppm.

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