CN102210915B - Biological method and equipment for degrading olaquindox serving as veterinary medicine and 3-methyl quinoxaline-2-carboxylic acid serving as metabolic marker thereof quickly - Google Patents
Biological method and equipment for degrading olaquindox serving as veterinary medicine and 3-methyl quinoxaline-2-carboxylic acid serving as metabolic marker thereof quickly Download PDFInfo
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- CN102210915B CN102210915B CN201110087109XA CN201110087109A CN102210915B CN 102210915 B CN102210915 B CN 102210915B CN 201110087109X A CN201110087109X A CN 201110087109XA CN 201110087109 A CN201110087109 A CN 201110087109A CN 102210915 B CN102210915 B CN 102210915B
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Abstract
The invention discloses a biological method and equipment for degrading olaquindox serving as a veterinary medicine and 3-methyl quinoxaline-2-carboxylic acid (MQCA) serving as a metabolic marker thereof quickly. The equipment consists of an air pump, a valve, a gravel layer, a biological compost reactor and a waste gas absorption device. The method comprises the following steps of: drying pig manure containing olaquindox and 3-methyl quinoxaline-2-carboxylic acid (MQCA) in the sun, crushing, sieving with a 200-mesh sieve, and putting into a biological compost of self-control equipment; adding a certain amount of straw (sieving with a 20-mesh sieve), regulating a ratio of carbon to nitrogen (C/N) to 27/1, regulating moisture content to 50 percent, and regulating ventilating flow to 0 cm<3>h<-1>; and fermenting for a period of time, so that the olaquindox and the 3-methyl quinoxaline-2-carboxylic acid (MQCA) in the biological compost are degraded effectively. The biological method and the equipment are simple in raw materials, low in cost, short in reaction time and high in removal efficiency of pollutants, and are favorable for popularization.
Description
Technical field
The invention belongs to the environmental pollution control technique field of veterinary drug, particularly antibiotic biodegradation method of quinoxaline veterinary drug and equipment.
Background technology
Olaquindox is a kind of quinoxaline veterinary drug antibiotic, in the seventies in 20th century by synthetic low toxicity, the special efficacy of West Germany Baeyer pharmaceutical factory research and have the growth improver for livestock and poultry of antibacterial action.Olaquindox is raw material with the ortho-nitraniline, gets through chemical synthesis, and its growth promotion mechanism rises pathogenic microorganism and kills and inhibitory action for through destroying protein synthesis system, folic acid and the RNA synzyme system of pathogenic microorganism.
Early 1980s, olaquindox begins to promote the use of in China as feed addictive.Existing research shows to fowl and fish, moderate to obvious accumulative toxicity and certain genetoxic are arranged, and the part fish are had obvious teratogenesis, and the U.S. and European Union forbid as feed addictive.In China, olaquindox still is widely used in fowl poultry and culture fishery.Addition in the aquaculture is about 50～100g/t, according to deliver 700,000,000 first-born pigs every year for sale, average 50% medicine excretes calculating, the annual olaquindox amount that gets in the environment is about 20,000 tons, potential problem of environmental pollution is very important.
The animal metabolism research of olaquindox shows; But 70% olaquindox follower ight soil and urine excrete; Olaquindox can reduce in animal body, oxidation and hydrolysis etc., and metabolic pathway is complicated, and metabolite is various; The metabolite of having identified has tens kinds, and the FAO (Food and Agriculture Organization of the United Nation) and World Health Organization regulation 3-methyl-Oxoquinoxaline-2-carboxylic acids (MQCA) are the residual marker of olaquindox at present.Flemming Ingerslev etc. has studied the biodegradation character of olaquindox in soil-ight soil system at lab simulation; The result show soil-ight soil system to the adsorptivity of olaquindox very a little less than; The degraded of olaquindox in soil-ight soil system is mainly biodegradation; Degradation half life is 5.8 ~ 8.8d, and soil types is different, and degradation half life does not show evident difference property.The soil environment behavioral study of olaquindox shows; Olaquindox is very fast in degraded in soil, and the soil degrading half-life is 15.1 ~ 77.0d, and microorganism plays a major role to its degraded; But soil to the olaquindox adsorptivity a little less than; Easily get into underground water and surface water, and research shows olaquindox not hydrolysis in the neutral aqueous solution at normal temperatures, so it is bigger to water body environment harm through eluviation with face of land runoff.
The biological compost technology is a kind of novel dystopy microorganism recovery technique; Finger directly mixes the rotten materials of easy heap such as branch, straw, muck, peat in the material that contaminated thing pollutes; For microorganism provides rich nutrient substances, and take oxygen content and acid-base value in the certain measure regulating system, to improve microbial activity; Fermentation process through after a while can make the most of pollutant that wherein contains be degraded.Complicated component in the pig manure contain protein, fats, organic acid, cellulose, hemicellulose and inorganic salts, and it is more to contain nitrogen, and the content of organic matter is high, is beneficial to microbial growth.For the pig manure that polluted by veterinary drug, adopting compost formula recovery technique is the comparatively ideal pre-treating method of its damage ratio of control.In recent years, receive organic pollution contaminated soil and pig manure with the reparation of biological compost method both at home and abroad, and obtain certain effect.
Summary of the invention
The object of the present invention is to provide a kind of repairing method of microorganism that receives solid matters such as olaquindox and 3-Jia based quinoxaline-2-carboxylic acid (MQCA) contaminated soil, pig manure, degradation of contaminant shortens the reaction time fast, improves the disposal ability of pollutant.
The present invention includes following steps:
Step 4, regulate and keep water content, fermentation.
The carbon-nitrogen ratio preferred proportion is 27/1; The reaction system water content is regulated and is kept 45% ~ 50%.
Reaction adopts aerobic condition or anaerobic condition all can; If adopt aerobic condition, ventilation flow rate is 0.1～0.15cm
3h
-1
The present invention also comprises a kind of equipment that adopts said method, comprises that air pump 1 is connected with reaction chamber 6 bottoms through valve 2, and the pallet of band passage is arranged at reaction chamber 6 bottoms, and grit layer 3 is positioned on the pallet, and pending biological shut-down system 4 is positioned at grit layer 3 top.
As required, also can be connected with exhaust gas absorption device 5 on reaction chamber 6 tops, exhaust gas absorption device 5 adopts active carbon to fill.
The raw material that the present invention adopts are simple, and cost is low, and the reaction time is short, and contaminant removal efficiency is high, is beneficial to popularization.
Description of drawings
Olaquindox was measured the MRM chromatogram during biology was piled when Fig. 1 began for reaction.
Fig. 2 adopts olaquindox mensuration MRM chromatogram in 2 days artifact heaps of the condition of supporting for reaction.
Fig. 3 adopts for reaction and detests in 3 days artifact heaps of the condition of supporting olaquindox and measure the MRM chromatogram.
Fig. 4 dynamically schemes for the metabolism of MQCA in the biology heap.
Fig. 5 is the reaction system equipment drawing.
1 is air pump among the figure, and 2 is valve, and 3 is sandy gravel stratum, and 4 is pending biological shut-down system, and 5 is exhaust gas absorption device, and 6 is reaction chamber, and 7 is gas delivery interface sketch map.
The specific embodiment
Embodiment 1:
The pig manure that does not contain olaquindox and metabolic markers 3-Jia based quinoxaline-2-carboxylic acid thereof is chosen in this reaction, and quantitative olaquindox is added in the back, so that treatment effect is accurately assessed.
1, ready reaction equipment; Comprise that air pump 1 is connected with the reaction chamber bottom through valve 2; The pallet of band passage is arranged at the reaction chamber bottom, and grit layer 3 is positioned on the pallet, and pending biological shut-down system 4 is positioned at grit layer 3 top; Reaction chamber top is connected with exhaust gas absorption device 5, and exhaust gas absorption device 5 adopts active carbon to fill.For the air that air pump 1 is carried can get in the reaction chamber 6 uniformly, reaction chamber 6 bottoms can add the air shooter that has a plurality of pores on the tube wall.Gas delivery interface sketch map 7 is for adopting the sketch map of crisscross gas carrier pipe.
2,2 processing of anaerobic and aerobic are set, each processing takes by weighing pig manure 4.5 kg, pulverizes dry (crossing 20 orders).
3, choose 0.5 kg wheat stalk and pulverize dry (crossing 20 orders).
4, evenly be spilled into the aqueous solution that 2.5 L contain olaquindox 5 mg/L with watering can, and constantly stirring, mixing are placed in the reaction chamber, the aerobic-anaerobic reaction condition is seen table 1, and the reaction system water content is regulated also and maintained 45% ~ 50%; The dynamic change of olaquindox and MQCA in the period sampling measuring pig manure.
Table 1 experimental design table
The result finds, under aerobic and the anaerobic condition olaquindox degraded in the biological heap of pig manure very fast, all detect behind aerobic 2d and the anaerobism 3d less than olaquindox content in the pig manure; Result such as Fig. 1, Fig. 2, Fig. 3; In the time of 37～41 days in the pig manure MQCA concentration reach maximum and be respectively 1.56 and 1.35 mg/kg; The conversion ratio that olaquindox changes into MQCA is between 40.7%～43.7 and 35.8%～37.9; During with 40 days in the pig manure MQCA concentration be initial concentration; The degraded of MQCA dynamic (like Fig. 2) in the period sampling measuring pig manure finds that anaerobism helps the degraded of MQCA, result such as table 2.
During with 40 days in the pig manure MQCA concentration be initial concentration, wherein, under the aerobic condition, the half-life of MQCA content is 24.8d, under the anaerobic condition, the half-life of MQCA content is 11.9d.
Table 2 MQCA is at the degradation characteristic of pig manure
| Handle | Time (d) | Degradation rate (%) | Ventilation flow rate (cm 3h -1) |
| Aerobic | 115d～120 | 90.5～92.3 | 0.1～0.15 |
| Anaerobism | 79d～81 | 84.5～86.1 | 0 |
Embodiment 2:
The pig manure that does not contain olaquindox and metabolic markers 3-Jia based quinoxaline-2-carboxylic acid thereof is chosen in this reaction, and quantitative olaquindox is added in the back, so that treatment effect is accurately assessed.
1, equipment is prepared with embodiment 1.
2, Anaerobic Treatment is set, takes by weighing pig manure 4.5 kg, pulverize dry (crossing 20 orders).
3, choose 0.5 kg wheat stalk and pulverize dry (crossing 20 orders).
4, evenly be spilled into the aqueous solution that 2.5 L contain olaquindox 5 mg/L with watering can, and constantly stirring, mixing are placed in the reaction chamber, the reaction system water content is regulated also and is maintained 45% ~ 50%; The dynamic change of olaquindox and MQCA in the period sampling measuring pig manure.
5, different carbon-nitrogen ratios being set handles and probes into the influence of different carbon-nitrogen ratios to olaquindox and MQCA degraded; The result shows that under the different carbon-nitrogen ratio conditions, olaquindox is all degraded rapidly; All degraded is complete in the 3d; In the time of 35～42 days in the pig manure MQCA concentration reach maximum between 1.32～1.56 mg/kg, the conversion ratio that olaquindox changes into MQCA is between 35.1%～37.9, MQCA degradation rate in the biological heap of the pig manure of different carbon-nitrogen ratios is different; During the 80d left and right sides, it is degraded in 27/1 o'clock the fastest (like table 3) in carbon-nitrogen ratio.
MQCA is at the degradation characteristic of pig manure under table 3 anaerobic condition
| Numbering | Carbon-nitrogen ratio | Time (d) | Degradation rate (%) |
| 1 | 18/1 | 79d～81 | 61..3～63.7 |
| 2 | 27/1 | 79d～81 | 84.5～86.1 |
| 3 | 35/1 | 79d～81 | 72.1～73.8 |
| 4 | 40/1 | 79d～81 | 63.6～66.0 |
Claims (7)
1. quick biological method of degraded veterinary drug olaquindox and metabolic markers 3-first based quinoxaline-2-carboxylic acid thereof is characterized in that may further comprise the steps:
Step 1, get the animal wastes or the soil that contain olaquindox and metabolic markers 3-Jia based quinoxaline-2-carboxylic acid thereof, pending after the drying and crushing;
Step 2, with the stalk drying and crushing;
Step 3, with pending thing and the abundant mixing of crop material, regulate between the carbon-nitrogen ratio 18/1 to 40/1;
Step 4, regulate and keep water content 45% ~ 50%, fermentation.
2. method according to claim 1 is characterized in that: described carbon-nitrogen ratio ratio is 27/1.
3. method according to claim 1 is characterized in that: regulate and keep reaction system water content 50%.
4. according to the described method of arbitrary claim in the claim 1 to 3, it is characterized in that: it is 0.1～0.15 cm that aerobic condition, blowing air flow are used in reaction
3h
-1
5. according to the described method of arbitrary claim in the claim 1 to 3, it is characterized in that: anaerobic condition is adopted in reaction.
6. equipment of realizing the said biological method of claim 1; It is characterized in that: comprise that air pump (1) is connected with reaction chamber (6) bottom through valve (2); The pallet of band passage is arranged at reaction chamber (6) bottom; Grit layer (3) is positioned on the pallet, and pending biological shut-down system (4) is positioned at grit layer (3) top.
7. equipment according to claim 6 is characterized in that: reaction chamber (6) top is connected with exhaust gas absorption device (5), and exhaust gas absorption device (5) adopts active carbon to fill.
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|---|---|---|---|
| CN201110087109XA CN102210915B (en) | 2011-04-08 | 2011-04-08 | Biological method and equipment for degrading olaquindox serving as veterinary medicine and 3-methyl quinoxaline-2-carboxylic acid serving as metabolic marker thereof quickly |
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| CN201110087109XA CN102210915B (en) | 2011-04-08 | 2011-04-08 | Biological method and equipment for degrading olaquindox serving as veterinary medicine and 3-methyl quinoxaline-2-carboxylic acid serving as metabolic marker thereof quickly |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201010642Y (en) * | 2007-02-13 | 2008-01-23 | 韩农 | Preprocessing device for stalk degradation |
| CN201074200Y (en) * | 2007-08-23 | 2008-06-18 | 复旦大学 | Device for degrading water body harmful algae by employing microorganism |
| CN101439919A (en) * | 2008-11-07 | 2009-05-27 | 张衍栋 | Method for innocent treatment of piggery feces |
| CN101759467A (en) * | 2008-12-24 | 2010-06-30 | 中国环境科学研究院 | Rural solid waste mixed aerobic composting method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201010642Y (en) * | 2007-02-13 | 2008-01-23 | 韩农 | Preprocessing device for stalk degradation |
| CN201074200Y (en) * | 2007-08-23 | 2008-06-18 | 复旦大学 | Device for degrading water body harmful algae by employing microorganism |
| CN101439919A (en) * | 2008-11-07 | 2009-05-27 | 张衍栋 | Method for innocent treatment of piggery feces |
| CN101759467A (en) * | 2008-12-24 | 2010-06-30 | 中国环境科学研究院 | Rural solid waste mixed aerobic composting method |
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