CN119456645A - Electron beam irradiation solid waste treatment method - Google Patents
Electron beam irradiation solid waste treatment method Download PDFInfo
- Publication number
- CN119456645A CN119456645A CN202411291808.XA CN202411291808A CN119456645A CN 119456645 A CN119456645 A CN 119456645A CN 202411291808 A CN202411291808 A CN 202411291808A CN 119456645 A CN119456645 A CN 119456645A
- Authority
- CN
- China
- Prior art keywords
- steroid hormone
- bacterial
- methanol
- electron beam
- steroid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000010894 electron beam technology Methods 0.000 title claims abstract description 21
- 238000009270 solid waste treatment Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003270 steroid hormone Substances 0.000 claims abstract description 82
- 230000001580 bacterial effect Effects 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 35
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000001110 calcium chloride Substances 0.000 claims abstract description 28
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000005865 ionizing radiation Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- AEMFNILZOJDQLW-QAGGRKNESA-N androst-4-ene-3,17-dione Chemical group O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 AEMFNILZOJDQLW-QAGGRKNESA-N 0.000 claims description 37
- 229960005471 androstenedione Drugs 0.000 claims description 37
- AEMFNILZOJDQLW-UHFFFAOYSA-N androstenedione Natural products O=C1CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC2=C1 AEMFNILZOJDQLW-UHFFFAOYSA-N 0.000 claims description 37
- 231100000987 absorbed dose Toxicity 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 3
- 239000003098 androgen Substances 0.000 abstract description 9
- 150000003431 steroids Chemical class 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 3
- 241000233866 Fungi Species 0.000 description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 13
- 238000000855 fermentation Methods 0.000 description 12
- 230000004151 fermentation Effects 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- SNMVJSSWZSJOGL-PLOWYNNNSA-N 9alpha-hydroxyandrost-4-en-3,17-dione Chemical compound O=C1CC[C@]2(C)[C@@]3(O)CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 SNMVJSSWZSJOGL-PLOWYNNNSA-N 0.000 description 5
- 229940030486 androgens Drugs 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- -1 chlorine ions Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- HGASFNYMVGEKTF-UHFFFAOYSA-N octan-1-ol;hydrate Chemical compound O.CCCCCCCCO HGASFNYMVGEKTF-UHFFFAOYSA-N 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 241000206601 Carnobacterium mobile Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002137 ultrasound extraction Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000010196 hermaphroditism Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010826 pharmaceutical waste Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000001082 somatic cell Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960003604 testosterone Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for treating solid waste by electron beam irradiation, in particular to a method for treating steroid hormone bacterial residues, which comprises the steps of 1) carrying out first mixing treatment on methanol and steroid hormone bacterial residues to be treated to obtain first mixed liquid, 2) adding calcium chloride into the first mixed liquid to obtain second mixed liquid, and 3) carrying out ionizing radiation treatment on the second mixed liquid so as to remove steroid hormone substances in the steroid hormone bacterial residues. The method can effectively remove steroid androgen pollutants in the bacterial residues.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to an electron beam irradiation solid waste treatment method.
Background
The steroid hormone medicine is a hormone medicine with a steroid structure in the molecule, and the basic structure of the steroid hormone medicine comprises 1 cyclopentane-polyhydrophenanthrene mother nucleus and 3 side chains. The parent nucleus is like a "field" and the 3 side chains are like "chuan" so that the compounds are represented like a "steroid" character. Steroid hormones mainly include sex hormones (estrogens and androgens), adrenocorticoids and protein assimilators, which are second only to antibiotics, and are widely used in the medical field. Among them, androgens represented by androstenedione, 9 α -hydroxyandrostenedione, and the like are key intermediates for synthesizing various steroid hormone drugs, and the market scale is enormous. The market for global androstenedione is estimated to be up to $2.1 billion by 2025.
The production method of steroid androgens mainly includes chemical synthesis method and microbial fermentation method. The chemical method has the advantages of complex synthesis process, high raw material cost, low yield and serious environmental pollution, and is gradually eliminated, and at present, the microbial fermentation method has become a mainstream technology for producing steroid hormone medicines. After fermentation is completed and steroid hormone medicine is extracted, a large amount of bacterial dreg waste is remained. The safe disposal and effective utilization of steroid hormone pharmaceutical waste has become one of the important factors restricting the increase of profit and the increase of productivity of enterprises.
Steroid hormones are an important class of endocrine disruptors (Endocrine disrupting chemicals, EDCs), which also cause hermaphrodites, reproductive disorders, etc. in aquatic organisms at very low concentrations, causing significant harm to the ecological environment and human health. EDCs, along with persistent organic pollutants, antibiotics and microplastics, are now a widely regarded "new pollutant" internationally.
The main components of the steroid hormone bacterial residues are mycelium, a culture medium and residual steroid hormone, and the pollution source is from the residual steroid hormone. If the bacteria residue can be removed from the bacteria residue, the harmless bacteria residue can be made into fertilizer to be reused as resources, so that the problems of steroid hormone bacteria residue treatment and disposal are solved. The steroid androgens have better thermal stability, and the structures of androgens including androstenedione, 9 alpha-hydroxy androstenedione, testosterone and the like remain substantially unchanged even under high temperature conditions of 165 ℃. Therefore, the pyrolysis type antibiotic fungus dreg treatment process commonly used in the pharmaceutical factories at present is not suitable for steroid hormone fungus dreg treatment.
The advanced oxidation technology represented by ultraviolet light catalysis and Fenton oxidation has good degradation and removal effects on steroid hormones in sewage, but has poor removal effects on the steroid hormones in bacterial residues. The fungus dreg is a viscous solid-liquid mixture, and the fungus dreg is difficult to penetrate into the fungus dreg for reaction by the conventional methods. Furthermore, steroid hormones are strongly hydrophobic compounds with a high octanol-water partition coefficient (Octanol-Water Partition Coefficient, K ow). Under the combined action of mechanisms such as hydrophobic distribution action, electrostatic interaction and the like, steroid hormone is firmly adsorbed and bound in bacterial dreg cell solids, and is difficult to react with active particles such as hydroxyl radicals and the like in water.
Thus, there is a need for an effective method of treating steroid hormone bacterial residues.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the invention aims to provide a steroid hormone bacterial dreg treatment method for efficiently removing steroid androgen pollutants in bacterial dreg.
In one aspect of the invention, the invention provides a method for treating steroid hormone bacterial residues. According to an embodiment of the invention, the method comprises:
1) Carrying out first mixing treatment on methanol and steroid hormone bacterial residues to be treated to obtain a first mixed solution;
2) Adding calcium chloride into the first mixed solution to obtain a second mixed solution;
3) And (3) carrying out ionizing radiation treatment on the second mixed solution so as to remove steroid hormone substances in the steroid hormone bacterial residues. The method can effectively remove steroid androgen pollutants in the bacterial residues.
According to an embodiment of the present invention, the above method may further include at least one of the following additional technical features:
according to the embodiment of the invention, the addition amount of the methanol solution is 2% -4% (methanol concentration/residual steroid hormone concentration).
According to the embodiment of the invention, the addition amount of the calcium chloride is 10% -20% (calcium chloride concentration/residual steroid hormone concentration).
According to an embodiment of the present invention, the ionizing radiation treatment is performed by subjecting the second mixed liquid to an ionizing radiation treatment by an electron beam.
According to the embodiment of the invention, the irradiation absorption dose of the electron beam is 25-50 kGy.
According to the embodiment of the invention, the steroid hormone bacterial residues are bacterial residues containing residual steroid hormone generated in the production process of the steroid hormone.
According to an embodiment of the invention, the steroid hormone is androstenedione or 9α -hydroxyandrostenedione.
According to the embodiment of the invention, the concentration of the residual androstenedione in the steroid hormone bacterial slag is 200mg/kg.
According to the embodiment of the invention, the concentration of the 9 alpha-hydroxy androstenedione remained in the steroid hormone bacterial slag is 500mg/kg.
According to an embodiment of the invention, the first mixing treatment is performed by vortex shaking.
According to an embodiment of the invention, the second mixing treatment is performed by vortex shaking.
In another aspect of the invention, the invention also provides a steroid hormone bacterial dreg treatment method. According to an embodiment of the invention, the method is as follows:
1) Adding methanol with a certain concentration into steroid hormone bacteria residues, carrying out vortex oscillation, and uniformly mixing;
2) Adding calcium chloride with a certain concentration into the mixture, carrying out vortex oscillation, and uniformly mixing;
3) And (3) conveying the mixture to an irradiation chamber of an electron accelerator, and carrying out ionization irradiation on the mixture by utilizing electron beams so as to degrade and remove steroid hormone substances in the bacterial residues. The method can effectively remove steroid androgen pollutants in the bacterial residues.
According to an embodiment of the present invention, the above method may further include at least one of the following additional technical features:
According to the embodiment of the invention, the electron beam is dense high-speed electron flow, has extremely high energy density and can penetrate into the interior of the fungus dreg for reaction. Methanol can be combined with steroid hormone molecules adsorbed on the cells of the bacteria through hydrophobic interaction, so that the steroid hormone molecules are removed from the bacteria residue solids and released into the solution. The calcium ions can replace steroid hormone molecules which are adsorbed on the bacterial dreg solids through ion exchange. Under the synergistic effect, steroid hormone is removed from the fungus dreg solid and released into the solution. Under the combined action of the direct radiation action of high-energy electron beams, active particles such as hydroxyl free radicals generated by electrons exciting water molecules and chlorine free radicals generated by irradiation exciting chlorine ions, steroid hormone pollutants in the bacterial residues are efficiently degraded and removed.
According to the embodiment of the invention, the steroid hormone bacterial dreg is bacterial dreg containing residual steroid hormone generated in the production process of the steroid hormone, and the steroid hormone is Androstenedione (AD) or 9 alpha-hydroxy androstenedione (OHAD).
According to the embodiment of the invention, the addition amount of the methanol solution is 2% -4% (methanol concentration/residual steroid hormone concentration).
According to the embodiment of the invention, the addition amount of the calcium chloride is 10% -20% (calcium chloride concentration/residual steroid hormone concentration).
According to the embodiment of the invention, the irradiation absorption dose of the electron beam is 25-50 kGy.
According to the embodiment of the invention, methanol and calcium chloride cooperate to remove steroid hormone molecules from solid cells of the bacterial residues through hydrophobic interaction and cation exchange, and the acidic environment (pH=4.7-5.7) of the bacterial residues of the steroid hormone is conducive to the generation of chlorine free radicals in the irradiation process, so that the removal of the steroid hormone in the bacterial residues is enhanced, and the removal rate of the steroid hormone can reach more than 99%. In the method provided by the embodiment of the invention, electron beam irradiation is performed at normal temperature, so that large-scale engineering application is easy to realize. The method provided by the invention is efficient and wide in application range, can be applied to steroid hormone bacteria residue treatment, and has wide application prospects in the field of harmful solid waste treatment.
According to an embodiment of the present invention, the electron beam generated by the electron accelerator is a dense high-speed electron stream with extremely high energy. Electron beam irradiation is an ionizing radiation technique. When the water molecules are excited by high-energy electron beam radiation, active particles such as hydroxyl radicals (OH) with strong oxidability, hydrated electrons (e aq -) with strong reducibility, hydrogen radicals (H) and the like are generated (as shown in formula 1, the value in brackets is the radiochemical yield G value of each active particle). Steroid hormone molecules may undergo oxidation-reduction reactions with these active particles to be degraded.
According to the embodiment of the invention, the degradation rate of the electron beam irradiation on steroid hormones such as AD and OHID in the aqueous solution is higher, but the degradation rate of the steroid hormones in the solid waste of the treated fungus dreg is obviously reduced. Adsorption of steroid hormone by the somatic cells significantly affects the irradiation degradation efficiency. Steroid hormones are strongly hydrophobic compounds with a high octanol-water partition coefficient (e.g. log k ow for AD of 2.75 and log k ow for ohad of 3.98). Under the combined action of mechanisms such as hydrophobic distribution action, electrostatic interaction and the like, steroid hormone is firmly adsorbed and bound in bacterial dreg cell solids, and is difficult to react with active particles such as hydroxyl radicals and the like in water. If steroid hormone molecules can be removed from the fungus dreg solids, the concentration of the steroid hormone molecules in the supernatant liquid is increased, and the irradiation degradation efficiency of the steroid hormone in the fungus dreg is hopeful to be improved.
According to embodiments of the present invention, methanol is an organic substance that is completely miscible with water, and is commonly used as a solubilizing agent for the organic substance. Methanol can be combined with steroid hormone molecules adsorbed on the cells of the bacteria through hydrophobic interaction, so that the steroid hormone molecules are removed from the bacterial dreg solids and released into the supernatant. In addition, in the acid environment of the bacterial residues, most of steroid hormone molecules exist in a positive valence ion form, and metal cations Ca 2+ can replace the steroid hormone molecules adsorbed on the bacterial residue solids through ion exchange, so that the concentration of the steroid hormone molecules in the supernatant is further improved, and the collision and reaction with active particles such as hydroxyl radicals in the solution are enhanced. Further, chloride ions can generate chlorine free radicals under the acidic condition of the bacterial residues through the following reaction, and the chlorine free radicals and steroid hormone molecules have higher reaction rate constants (the order of magnitude is 10 10 L/mol s). Steroid hormone molecules are efficiently degraded under the combined action of active particles such as hydroxyl radicals, chlorine radicals, hydrated electrons and the like.
Cl-+·OH→ClOH·- k＝4.3×109L/mols (2)
ClOH·-+H+→Cl·+H2O k＝2.1×109L/mols (3)
Detailed Description
The following examples are illustrative and are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting in any way.
Example 1
The AD fermentation fungus dreg is taken from a certain pharmaceutical enterprise in Hebei province of China, the water content of the AD fermentation fungus dreg is 79%, the pH value of the AD fermentation fungus dreg is 5.6, the Total Solid (TS) content of the AD fermentation fungus dreg is 212g/kg, the ratio of Volatile Solid (VS)/TS is 85%, and the concentration of residual AD is about 200mg/kg. Methanol was commercially available in analytical purity. Calcium chloride is commercially available in analytical purity.
About 10g of AD fermentation fungus dreg is weighed, 4mg/L (2%), 8mg/L (4%), 12mg/L (6%) of methanol are respectively added, and vortex shaking and mixing are uniform. About 10g of AD fermentation fungus dreg is weighed, 4mg/L of methanol is added, 10mg/L (5%), 20mg/L (10%) and 40mg/L (20%) of calcium chloride are respectively added, and vortex vibration and uniform mixing are carried out. And (3) placing the uniformly mixed fungus dreg sample into a sample bag, and conveying the sample to an irradiation chamber of an electron accelerator by using a conveying belt for irradiation. And (3) simultaneously irradiating and comparing the pure bacterial dreg samples without adding methanol and calcium chloride and the bacterial dreg samples with calcium chloride.
Different radiation absorption doses of 10kGy, 25kGy and 50kGy are obtained by controlling the beam intensity of the electron beam and the transmission speed of the sample. The detection index is the concentration of steroid hormone AD in the fungus dreg before and after electron beam irradiation.
Extracting residual AD in the bacterial residues by acetonitrile, and detecting by liquid chromatography.
The AD extraction method of the bacterial residues comprises the steps of placing about 0.2g of bacterial residues in a 15mL polypropylene centrifuge tube, adding 5mL acetonitrile, carrying out vortex oscillation for 3min, and carrying out ultrasonic-assisted extraction for 20min. Centrifuging at 10000rpm for 10min, collecting supernatant, filtering with 0.22 μm filter membrane, and diluting the filtered solution to appropriate multiple for high performance liquid chromatography detection.
Wherein the high performance liquid chromatograph is Agilent 1200, agilent company, U.S., and the chromatographic column is XDB-C18 reversed phase column with column temperature of 30deg.C. Mobile phase 0.1% formic acid aqueous solution and acetonitrile (mixing ratio 30:70). The detector is an ultraviolet detector, and the AD detection wavelength is 245nm.
The removal rate of AD in the bacterial residues under the conditions of different absorption doses, methanol and calcium chloride addition amounts are shown in Table 1. It can be seen that the AD removal rate can reach 79% when the irradiation absorbed dose is 10kGy, but the AD removal rate is improved slightly with further increase of the absorbed dose. When the absorbed dose is 50kGy, the AD removal rate is 90%, and a relatively high concentration of AD (about 20 mg/L) remains in the bacterial residues.
When the addition amount of methanol is 2% and 4%, the AD removal efficiency can be remarkably improved. When the absorbed dose is 50kGy, the AD removal rate can reach 93% -96%. However, if the methanol dose is too high (6%), the AD removal rate is reduced. Methanol can react with hydroxyl radical generated by water molecule irradiation, and if the concentration is too high, the quenching effect on the hydroxyl radical is larger than the promotion effect of the enhanced AD desorption and dissolution, so that the AD removal efficiency is reduced.
When the addition amount of the methanol is 2% -4%, the calcium chloride is continuously added, and the AD removal efficiency is further improved. When the addition amount of methanol is 2% -4%, the addition amount of calcium chloride is 20%, and the absorption dose is 25% -50 kGy, the AD removal rate can reach more than 99%. The calcium chloride added alone has a certain promotion effect on AD degradation. The calcium chloride addition was 20% and the AD removal rate was 92% at an absorbed dose of 50 kGy.
TABLE 1 removal rate of AD in bacterial residues under different experimental conditions (%)
Example 2
OHAD the fermentation residue was obtained from a pharmaceutical company in Hubei province in China, and had a water content of 37%, a pH value of 4.6, a Total Solids (TS) content of 332g/kg, a Volatile Solids (VS)/TS ratio of 99% and a residual OHAD concentration of about 500mg/kg. Methanol was commercially available in analytical purity. Calcium chloride is commercially available in analytical purity.
About 10g OHAD of fermentation residues are weighed, 10mg/L (2%), 20mg/L (4%), 30mg/L (6%) of methanol are respectively added, and vortex shaking and mixing are uniform. About 10g OHAD of fermentation residues are weighed, 10mg/L of methanol is added, 25mg/L (5%), 50mg/L (10%) and 100mg/L (20%) of calcium chloride are added respectively, and vortex vibration and uniform mixing are carried out. And (3) placing the uniformly mixed fungus dreg sample into a sample bag, and conveying the sample to an irradiation chamber of an electron accelerator by using a conveying belt for irradiation. And (3) simultaneously irradiating and comparing the pure bacterial dreg samples without adding methanol and calcium chloride and the bacterial dreg samples with calcium chloride.
Different radiation absorption doses of 10kGy, 25kGy and 50kGy are obtained by controlling the beam intensity of the electron beam and the transmission speed of the sample. The detection index is the concentration of steroid hormone OHAD in the fungus dreg before and after electron beam irradiation.
Extracting OHAD remained in the fungus dreg by acetonitrile, and detecting by liquid chromatography.
The method for extracting OHAD of fungus dreg comprises the steps of placing about 0.2g of fungus dreg in a 15mL polypropylene centrifuge tube, adding 5mL acetonitrile, carrying out vortex oscillation for 3min, and carrying out ultrasonic-assisted extraction for 20min. Centrifuging at 10000rpm for 10min, collecting supernatant, filtering with 0.22 μm filter membrane, and diluting the filtered solution to appropriate multiple for high performance liquid chromatography detection.
Wherein the high performance liquid chromatograph is Agilent 1200, agilent company, U.S., and the chromatographic column is XDB-C18 reversed phase column with column temperature of 30deg.C. Mobile phase 0.1% formic acid aqueous solution and acetonitrile (mixing ratio 30:70). The detector is an ultraviolet detector, OHAD detection wavelength is 254nm.
The removal rate of OHAD in the bacterial residues under the conditions of different absorption doses, methanol and calcium chloride addition amounts are shown in table 2. It can be seen that the OHAD removal rate was 74% at 10kGy of radiation absorbed dose, but the OHAD removal rate was improved by a smaller margin as the absorbed dose was further increased. When the absorbed dose is 50kGy, the OHAD removal rate is 88%, and OHAD (about 60 mg/L) still remains in the bacterial residues at a higher concentration.
When the addition amount of the methanol is 2% -4%, the removal efficiency of OHAD can be remarkably improved. When the absorbed dose is 50kGy, the OHAD removal rate can reach 90% -95%. However, if the methanol dosage is too high (6%), OHAD removal rate is reduced. Methanol can react with hydroxyl radical generated by water molecule irradiation, if the concentration is too high, the quenching effect on the hydroxyl radical is larger than the promotion effect generated by the enhancement OHAD dissolution, so that the OHAD removal efficiency is reduced.
When the addition amount of the methanol is 2% -4%, the calcium chloride is continuously added, and the removal rate of OHAD is further improved. When the addition amount of methanol is 4%, the addition amount of calcium chloride is 20% and the absorption dose is 25-50 kGy, the removal rate of OHAD can reach more than 99%. The calcium chloride is added singly to have a certain promotion effect on OHAD degradation. The calcium chloride addition amount is 20%, and the OHAD removal rate is 91% when the absorbed dose is 50 kGy.
TABLE 2 removal rate of OHAD from bacterial residues under different experimental conditions (%)
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Claims (10)
1. A method for treating steroid hormone bacterial residues is characterized by comprising the following steps:
1) Carrying out first mixing treatment on methanol and steroid hormone bacterial residues to be treated to obtain a first mixed solution;
2) Adding calcium chloride into the first mixed solution to obtain a second mixed solution;
3) And (3) carrying out ionizing radiation treatment on the second mixed solution so as to remove steroid hormone substances in the steroid hormone bacterial residues.
2. The method according to claim 1, wherein the amount of methanol added is 2% -4%.
3. The method according to claim 1, wherein the amount of calcium chloride added is 10% -20%.
4. The method according to claim 1, wherein the ionizing radiation treatment is performed by subjecting the second mixed liquid to an ionizing radiation treatment by an electron beam.
5. The method according to claim 4, wherein the irradiation absorbed dose of the electron beam is 25kgy to 50kgy.
6. The method according to claim 1, wherein the steroid hormone bacterial residue is a bacterial residue containing residual steroid hormone generated during the production of the steroid hormone.
7. The method of treatment according to claim 1, wherein the steroid hormone is androstenedione or 9 a-hydroxyandrostenedione.
8. The method according to claim 1, wherein the concentration of androstenedione remaining in the steroid hormone bacterial slag is 200mg/kg.
9. The method according to claim 1, wherein the concentration of 9 a-hydroxyandrostenedione remaining in the steroid hormone bacterial dreg is 500mg/kg.
10. The method according to claim 1, wherein the first mixing treatment is performed by vortex shaking;
optionally, the second mixing treatment is performed by vortex shaking.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411291808.XA CN119456645A (en) | 2024-09-14 | 2024-09-14 | Electron beam irradiation solid waste treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411291808.XA CN119456645A (en) | 2024-09-14 | 2024-09-14 | Electron beam irradiation solid waste treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN119456645A true CN119456645A (en) | 2025-02-18 |
Family
ID=94580553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411291808.XA Pending CN119456645A (en) | 2024-09-14 | 2024-09-14 | Electron beam irradiation solid waste treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN119456645A (en) |
-
2024
- 2024-09-14 CN CN202411291808.XA patent/CN119456645A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kan et al. | High frequency discharge plasma induced plasticizer elimination in water: Removal performance and residual toxicity | |
| Hu et al. | Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2 | |
| Zambrano et al. | Removal of a mixture of veterinary medicinal products by adsorption onto a Scenedesmus almeriensis microalgae-bacteria consortium | |
| Zhan et al. | Remediation of perfluorooctanoic acid (PFOA) polluted soil using pulsed corona discharge plasma | |
| Hijosa-Valsero et al. | Removal of cyanide from water by means of plasma discharge technology | |
| Ding et al. | Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation | |
| Huang et al. | Hydroxylamine activated by discharge plasma for synergetic degradation of tetracycline in water: Insight into performance and mechanism | |
| CN111115745B (en) | A method for degrading organic pollutants in water by ionizing radiation | |
| Liang et al. | Breaking rate-limiting steps in a red mud-sewage sludge carbon catalyst activated peroxymonosulfate system: Effect of pyrolysis temperature | |
| Qian et al. | Carbonaceous composite membranes for peroxydisulfate activation to remove sulfamethoxazole in a real water matrix | |
| CN103482733A (en) | Method of removing sulfonamide antibiotics in water by utilizing ionization radiation technology | |
| Cheng et al. | Effects of the natural colloidal particles from one freshwater lake on the photochemistry reaction kinetics of ofloxacin and enrofloxacin | |
| Salman et al. | Removal of diclofenac from aqueous solution on apricot seeds activated carbon synthesized by pyro carbonic acid microwave | |
| Zheng et al. | Degradation of pesticide wastewater with simultaneous resource recovery via ozonation coupled with anaerobic biochemical technology | |
| Zhang et al. | Remediation of atrazine-polluted soil using dielectric barrier discharge plasma and biochar sequential batch experimental technology | |
| Zheng et al. | Study on catalytic mechanisms of Fe3O4-rGOx in three typical advanced oxidation processes for tetracycline hydrochloride degradation | |
| Zhang et al. | Adsorption-reduction coupling mechanism and reductive species during efficient florfenicol removal by modified biochar supported sulfidized nanoscale zerovalent iron | |
| Sang et al. | Enhanced norfloxacin removal from sludge by dielectric barrier discharge plasma synthesis with Fe3O4/g-C3N4 | |
| CN119456645A (en) | Electron beam irradiation solid waste treatment method | |
| Li et al. | High efficiency and rapid treatment of naproxen sodium wastewater by dielectric barrier discharge coupled with catalysis | |
| CN105271604A (en) | Method for removing PPCPs in water body | |
| Ling et al. | Effect of dose rate on degradation of 2, 6-dichlorophenol by electron beam irradiation | |
| Zhang et al. | Removal of refractory organic matter from landfill-contaminated groundwater by a permeable reactive barrier coupled with an Fe0/PMS advanced oxidation system | |
| Zhang et al. | Removal of refractory organic compounds from bio-treated landfill leachate using a Fe0-H2O2-MoS2 process under continuous operation mode | |
| CN116002893A (en) | Pesticide wastewater treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |