CN103214281A - Method for performing chemical innocent treatment on erythromycin waste residues and using erythromycin waste residues for producing organic fertilizer - Google Patents
Method for performing chemical innocent treatment on erythromycin waste residues and using erythromycin waste residues for producing organic fertilizer Download PDFInfo
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- CN103214281A CN103214281A CN2013101624050A CN201310162405A CN103214281A CN 103214281 A CN103214281 A CN 103214281A CN 2013101624050 A CN2013101624050 A CN 2013101624050A CN 201310162405 A CN201310162405 A CN 201310162405A CN 103214281 A CN103214281 A CN 103214281A
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- erythromycin
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Abstract
The invention discloses a method for performing chemical innocent treatment on erythromycin waste residues and using the erythromycin waste residues for producing an organic fertilizer. The method is characterized by comprising the steps of adding 0.01-0.30mol acid to raw erythromycin waste residue liquid per liter, keeping at the room temperature for 4-6 hours for hydrolysis, adding alkali for neutralizing the liquid to be neutral, then adding an auxiliary material, mixing, stirring, pelleting, drying and obtaining the organic fertilizer. According to the method, a chemical degradation technology is adopted for treating the erythromycin waste residues, so that erythromycin residual in the waste residues can be reduced to below 10mg/kg; a degradation rate of the chemical degradation technology can achieve above 99.6%; in addition, the organic fertilizer in the erythromycin waste residues is hardly wasted; the innocent treatment is realized; the erythromycin waste residues are then used for preparing the organic fertilizer, so that the erythromycin waste residues are recycled; the purpose of comprehensive utilization is achieved; the method is simple to operate and high in treatment efficiency; the daily treatment capacity is high; the erythromycin waste residue liquid with 4-6 times effective volume of a container can be obtained; large-scale treatment can be realized; and the method has a significant economic benefit and a significant social benefit.
Description
Technical field
The present invention relates to a kind of processing and utilizing method of erythromycin bacterium slag, particularly a kind of method that adopts chemical method that erythromycin bacterium slag is handled and utilized.
Background technology
Erythromycin bacterium slag mainly is to be raw material with starch, soybean cake powder etc., add the waste residue that the erythromycin bacterial classification produces behind fermentative production erythromycin, except containing a large amount of moisture, its main component is residual starch and Dian Fentang, residual soybean cake powder, mycelium and a spot of erythromycin are residual, concentration in bacterium slag stoste is (0.3～0.4) g/L approximately, looks the water content difference, and the content of being converted into dried slag is about (2～4) g/kg.The waste residue that produces when using zinc sulfate as flocculation agent in production technique also contains many zinc element.Raw material sources from erythromycin bacterium slag, harmful element such as contained heavy metal and material can be high in the bacterium slag, serve environmental testing service department of (Shanghai) Co., Ltd. through logical mark standard technique and measure, confirmed the concentration limit of the amount of bacterium slag institute containing metal far below the metallic element of " GB 18877 organic-inorganic composite fertilizers " middle regulation.
Erythromycin bacterium slag gives out a kind of specific peculiar smell, and bacterium slag organic content height can not caused Secondary Fermentation if do not dispose to discard arbitrarily, and the color blackening produces foul smell, attracts a large amount of flies, and environment is very abominable.Along with the raising of people's environmental consciousness and the increasing of national environmental protection renovation dynamics, numerous enterprises is developed bacterium slag drying plant one after another, and the bacterium slag is dried to moisture less than 10% dry product, adds a little other materials again, makes animal-feed.But residual a small amount of microbiotic and degradation product thereof in the bacterium slag is under suspicion this animal-feed.Though antibiotic inactivation substantially after drying, its enrichment in animal body, have influence on again human itself, make the people produce resistance.In February, 2002, the Ministry of Agriculture, the Ministry of Health, No. 176 bulletin of National Drug Administration were classified the microbiotic filter residue in the types of drugs catalogue of forbidding using as in feed and animal drinking water.From on August 23rd, 2002, be illegal, illegal operation activity with dried bacterium slag as fodder production, sale again, will be subjected to the corresponding punishment of rules.
According to revised " national Hazardous wastes register " in 2008, antibiotic bacterium dregs belonged to the substratum refuse in the pharmaceutical chemicals production of raw medicine process, must manage by Hazardous wastes.Antibiotic bacterium dregs contains residual antibiotic and metabolic intermediate etc., it is a kind of special Hazardous wastes, as mishandling, can produce potential harm to ecotope and HUMAN HEALTH, its harm has characteristics such as disguise, hysteresis quality, accumulative total property, synergetic property and related property.
Realistic problem such as big at the erythromycin bacterium slag generation, that intractability is big, " encouraging reutilization technology, innoxious process for treating, the comprehensive utilization technique of exploitation zymophyte slag in the production technique " policy and suggestion that propose in " pharmaceutical industry pollution prevention technique policy " (exposure draft), utilize membrane separation technique to replace the zinc sulfate flocculation technique in the erythromycin production technique, no longer include the existence of zinc element in the bacterium slag.
But, for wherein residual antibiotic and metabolic intermediate, present processing mode has the bio-modification of carrying out, promptly by inoculation selectivity mixed bacterial and compound enzymic preparation solid state fermentation, after the modification again as the substratum of erythromycin and macrolide antibiotics fermentation, it as application number 2007100527715 Chinese patent application, this processing mode, the final erythromycin bacterium slag that still can obtain microbiotic and metabolic intermediate, can not finally realize harmless treatment, be that residual erythrocin and metabolic intermediate in the bacterium slag can not finally be removed, still exist ecological, healthy hidden danger.Also have report that wherein residual erythrocin and mesostate thereof carried out separation and Extraction, but this mode complex process, cost height is difficult to the bulky erythromycin bacterium slag of industrial treatment.
Summary of the invention
Goal of the invention of the present invention is: at the problem of above-mentioned existence, provide a kind of economy, harmless treatment erythromycin bacterium slag and use it for the method for producing fertilizer efficiently.
The technical solution used in the present invention is such: harmless treatment of a kind of erythromycin bacterium dreg chemistry and the method that is used to produce fertilizer, the acid that in every liter of erythromycin bacterium slag stoste, adds 0.01～0.30mol, and keep 4-6h to be hydrolyzed, add alkali after the hydrolysis again and be neutralized to neutrality, add auxiliary material then and mix stirring, granulation, oven dry promptly makes fertilizer.
Find through a large amount of experiments, in bacterium slag liquid, add suitable acid amount, can make in the erythromycin bacterium slag residual erythrocin in the short period of time degradation rate reach more than 99%, simultaneously the materials such as organic matter in the erythromycin bacterium slag are not almost destroyed, after adding suitable auxiliary material, the erythromycin bacterium slag after the degraded can be further used for producing fertilizer.
As preferably: the concentration of the acid of use is more preferably greater than 60%.The volume of handling back bacterium slag liquid is unlikely to increase too much, consumes energy less when oven dry.
As preferably: described acid is mineral acid.
From cost consideration, adopt the mineral acid cost cheaper, also easier popularization, realization mass-producing are handled.
Further: described mineral acid is nitric acid or phosphoric acid.
Adopt nitric acid or phosphoric acid, be fully used when N element wherein or P element can be used to prepare fertilizer after processing.
As preferably: described alkali is mineral alkali.
From cost consideration, adopt the mineral alkali cost cheaper, also easier popularization, realization mass-producing are handled.
Further: described mineral alkali is potash or ammonia.
Adopt potash or ammonia, be fully used when K element wherein or N element can be used to prepare fertilizer after processing.
As preferably: described auxiliary material is at least a in humic acid or the wilkinite.Take all factors into consideration from the nutrition of fertilizer and the composition of the bacterium slag after the processing, add humic acid or wilkinite and can obtain fertilizer balanced in nutrition, and can give full play to the effect and the suitable for making particle fertilizer of various moietys.
Further: according to the mass percent meter, the product water ratio after the oven dry is less than 20%.
Further: by the product 60% after the oven dry, the ratio of humic acids 30%, wilkinite 10% is made fertilizer.The fertilizer quality that obtains is more excellent.
In sum; owing to adopted technique scheme; the invention has the beneficial effects as follows:: adopt chemical degradation technical finesse erythromycin bacterium slag; make residual the reducing to below 10 mg/kg of erythromycin in the bacterium slag; its degradation rate can reach more than 99.6 %; organic matter does not wherein almost have loss simultaneously; realize harmless treatment, use it for the making fertilizer then, make its resource utilization; reach the purpose of comprehensive utilization; present method is simple to operate, and processing efficiency height, day output can reach 4～6 times of bacterium slag stostes of container effective volume; thereby can realize the mass-producing processing, have remarkable economic efficiency and social benefit.
Embodiment
Below the present invention is done detailed explanation.
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Embodiment 1:
Get 1L erythromycin bacterium slag stoste, wherein the erythromycin residual quantity is 365mg, and organic content is 59.4g, water ratio 85% adds 69% nitric acid 0.63mL, and acid concentration is 0.01mol/L, stir evenly posthydrolysis 6h, after 0.56 gram neutralization of hydro-oxidation potassium and the oven dry, by butt, get hydrolysate 151g, organic content is 39.3%, heavy 59.3g, and 10% pH value of water solution is 7.8, erythromycin is residual to be 9.3 mg/kg, and the degradation rate of erythromycin is 99.6%.Add humic acid (soil ulmin 60%, moisture 30%) 75.5g, wilkinite (water ratio 23%) 25.4 then, mix and stir, granulation, oven dry promptly makes fertilizer again, and the composition of gained fertilizer is as follows:
Project measured value standard
Total nutrient (nitrogen+Vanadium Pentoxide in FLAKES+potassium oxide)/%(is in butt) 5.7 〉=4
Organic matter/% (in butt) 46.8 〉=30
Moisture/% 10.5≤20
PH value 7.5 5.5-8
Erythromycin is residual/mg/kg (in butt) 6.3-
Embodiment 2
Get 1L erythromycin bacterium slag stoste, wherein the erythromycin residual quantity is 365mg, and organic content is 59.4g, water ratio 85% adds 69% nitric acid 1.9mL, and acid concentration is 0.03mol/L, stir evenly posthydrolysis 6h, after 1.7 gram neutralizations of hydro-oxidation potassium and the oven dry, by butt, get hydrolysate 153g, organic content is 38.8%, heavy 59.4g, and 10% pH value of water solution is 7.5, erythromycin is residual to be 5.2 mg/kg, and the degradation rate of erythromycin is 99.8%.Add humic acid (soil ulmin 60%, moisture 30%) 76.5g, wilkinite (water ratio 23%) 25.5g then, mix and stir, granulation, oven dry promptly makes fertilizer, and the composition of gained fertilizer is as follows:
Project measured value standard
Total nutrient (nitrogen+Vanadium Pentoxide in FLAKES+potassium oxide)/%(is in butt) 6.6 〉=4
Organic matter/% (in butt) 46.6 〉=30
Moisture/% 11.5≤20
PH value 7.3 5.5-8
Erythromycin is residual/mg/kg (in butt) 3.5-
Embodiment 3
1L erythromycin bacterium slag stoste, wherein the erythromycin residual quantity is 365mg, organic content is 59.4g, water ratio 85% adds 69% nitric acid 18.8mL, and acid concentration is 0.3mol/L, stir evenly posthydrolysis 4h, after 16.8 gram neutralizations of hydro-oxidation potassium and the oven dry, by butt, get hydrolysate 180g, organic content is 32.9%, heavy 59.2g, and 1% pH value of water solution is 7.4, erythromycin is residual to be 4.6 mg/kg, and the degradation rate of erythromycin is 99.8%.Add humic acid (soil ulmin 60%, moisture 30%) 90g, wilkinite (water ratio 23%) 30g then, mix and stir, granulation, oven dry promptly makes fertilizer, and the composition of gained fertilizer is as follows:
Project measured value standard
Total nutrient (nitrogen+Vanadium Pentoxide in FLAKES+potassium oxide)/%(is in butt) 10.7 〉=4
Organic matter/% (in butt) 42.5 〉=30
Moisture/% 10.8≤20
PH value 6.9 5.5-8
Erythromycin is residual/mg/kg (in butt) 3.1-
Embodiment 4
1.5m
3Erythromycin bacterium slag stoste, wherein the erythromycin residual quantity is 548g, organic content is 61.4kg, water ratio 90% adds 60% industrial nitric acid, 24 kg, and acid concentration is 0.15mol/L, stir evenly posthydrolysis 5h, after hydro-oxidation potassium 18.6kg neutralization and the oven dry, by butt, get hydrolysate 173 kg, organic content is 35.4%, heavy 61.2kg, and 10% pH value of water solution is 7.2, erythromycin is residual to be 3.7mg/kg, and the degradation rate of erythromycin is 99.9%.Add humic acid (soil ulmin 60%, moisture 30%) 96kg, wilkinite (water ratio 23%) 30kg then, mix and stir, granulation, oven dry promptly makes fertilizer, and the composition of gained fertilizer is as follows:
Project measured value standard
Total nutrient (nitrogen+Vanadium Pentoxide in FLAKES+potassium oxide)/%(is in butt) 8.7 〉=4
Organic matter/% (in butt) 44.3 〉=30
Moisture/% 8.9≤20
PH value 7.0 5.5-8
Erythromycin is residual/mg/kg (in butt) 2.4-
Embodiment 5
3m
3Erythromycin bacterium slag stoste, wherein the erythromycin residual quantity is 1182g, organic content is 162kg, water ratio 88% adds 85% industrial phosphoric acid 35kg, and acid concentration is 0.1mol/L, stir evenly posthydrolysis 5h, after logical ammonia is neutralized to neutral also oven dry, by butt, get hydrolysate 390kg, organic content is 41.3%, weighs 161.1 kg, and 10% pH value of water solution is 7.0, erythromycin is residual to be 5.1mg/kg, and the degradation rate of erythromycin is 99.8%.Add humic acid (soil ulmin 60%, moisture 30%) 210k g, wilkinite (water ratio 23%) 70kg then, mix and stir, granulation, oven dry promptly makes fertilizer, and the composition of gained fertilizer is as follows:
Project measured value standard
Total nutrient (nitrogen+Vanadium Pentoxide in FLAKES+potassium oxide)/%(is in butt) 6.1 〉=4
Organic matter/% (in butt) 48.6 〉=30
Moisture/% 10.2≤20
PH value 6.8 5.5-8
Erythromycin is residual/mg/kg (in butt) 3.4-.
Claims (8)
1. erythromycin bacterium dreg chemistry harmless treatment and the method that is used to produce fertilizer, it is characterized in that: the acid that in every liter of erythromycin bacterium slag stoste, adds 0.01～0.30mol, and keep 4-6h to be hydrolyzed at normal temperatures, add alkali after the hydrolysis again and be neutralized to neutrality, add auxiliary material then and mix stirring, granulation, oven dry promptly makes fertilizer.
2. a kind of erythromycin bacterium dreg chemistry according to claim 1 harmless treatment and the method that is used to produce fertilizer is characterized in that: employed acid is the acid of higher concentration.
3. a kind of erythromycin bacterium dreg chemistry according to claim 2 harmless treatment and the method that is used to produce fertilizer is characterized in that: described acid is mineral acid.
4. a kind of erythromycin bacterium dreg chemistry according to claim 3 harmless treatment and the method that is used to produce fertilizer is characterized in that: described mineral acid is nitric acid or phosphoric acid.
5. a kind of erythromycin bacterium dreg chemistry according to claim 1 harmless treatment and the method that is used to produce fertilizer is characterized in that: described alkali is mineral alkali.
6. a kind of erythromycin bacterium dreg chemistry according to claim 4 harmless treatment and the method that is used to produce fertilizer is characterized in that: described mineral alkali is potash or ammonia.
7. a kind of erythromycin bacterium dreg chemistry according to claim 1 harmless treatment and the method that is used to produce fertilizer is characterized in that: described auxiliary material is at least a in humic acids or the wilkinite.
8. a kind of erythromycin bacterium dreg chemistry according to claim 6 harmless treatment and the method that is used to produce fertilizer is characterized in that: according to the mass percent meter, and the product 60% after the oven dry, humic acids 30%, wilkinite 10%.
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| CN103553805A (en) * | 2013-10-31 | 2014-02-05 | 宁夏启元药业有限公司 | Method for producing organic fertilizer by using erythromycin waste residue and tetracycline urea double salt mother liquor |
| CN105016790A (en) * | 2015-07-10 | 2015-11-04 | 伊犁川宁生物技术有限公司 | Processing method of erythrocin bacterium residues |
| CN105924271A (en) * | 2016-04-22 | 2016-09-07 | 潘峰 | Biological organic fertilizer produced by using erythromycin bacterium residues and preparation method of biological organic fertilizer |
| CN106925596A (en) * | 2015-12-30 | 2017-07-07 | 中粮营养健康研究院有限公司 | A kind of handling process of antibiotic bacterium dregs |
| CN106925595A (en) * | 2015-12-30 | 2017-07-07 | 中粮营养健康研究院有限公司 | A kind of handling process of antibiotic bacterium dregs |
| CN106925597A (en) * | 2015-12-30 | 2017-07-07 | 中粮营养健康研究院有限公司 | A kind of handling process of antibiotic bacterium dregs |
| CN107311729A (en) * | 2017-08-04 | 2017-11-03 | 哈尔滨工业大学 | A kind of method that utilization lincomycin fungi residues produce organic fertilizer |
| CN107324905A (en) * | 2017-08-04 | 2017-11-07 | 哈尔滨工业大学 | A kind of method that utilization erythromycin bacterium slag produces organic fertilizer |
| CN107337497A (en) * | 2017-08-11 | 2017-11-10 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using aminoglycoside antibiotics bacteria residue |
| CN107337496A (en) * | 2017-08-09 | 2017-11-10 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using tylosin dreg |
| CN107353114A (en) * | 2017-08-09 | 2017-11-17 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue |
| CN107382419A (en) * | 2017-08-11 | 2017-11-24 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using macrolide antibiotic bacterium dregs |
| CN107500984A (en) * | 2017-09-21 | 2017-12-22 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using Fenton process processing antibiotic bacterium dregs |
| CN107522525A (en) * | 2017-09-21 | 2017-12-29 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using ozone processing antibiotic bacterium dregs |
| CN107522546A (en) * | 2017-08-30 | 2017-12-29 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using polypeptide antibiotics bacteria residue |
| CN109776238A (en) * | 2019-03-29 | 2019-05-21 | 山东睿智医药科技有限公司 | A method of functional organic fertilizer is produced using cephalosporin filter residue |
| CN110951637A (en) * | 2019-11-28 | 2020-04-03 | 宁夏泰益欣生物科技有限公司 | Novel method for treating erythrocin fungi residues |
| CN111440022A (en) * | 2020-03-17 | 2020-07-24 | 同济大学 | Preparation method and application of multi-element composite water-soluble fertilizer solid powder by using antibiotic fungi residues |
| CN112337033A (en) * | 2020-11-24 | 2021-02-09 | 内蒙古科技大学 | Harmless treatment method of abamectin slag, product and application of product as sandy soil modifier |
| CN114573379A (en) * | 2022-03-22 | 2022-06-03 | 丽珠集团福州福兴医药有限公司 | Method for fertilizing antibiotic mushroom dregs and organic fertilizer |
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| CN103553805A (en) * | 2013-10-31 | 2014-02-05 | 宁夏启元药业有限公司 | Method for producing organic fertilizer by using erythromycin waste residue and tetracycline urea double salt mother liquor |
| CN105016790A (en) * | 2015-07-10 | 2015-11-04 | 伊犁川宁生物技术有限公司 | Processing method of erythrocin bacterium residues |
| CN106925597B (en) * | 2015-12-30 | 2020-04-17 | 中粮营养健康研究院有限公司 | Treatment process of antibiotic fungi residues |
| CN106925596A (en) * | 2015-12-30 | 2017-07-07 | 中粮营养健康研究院有限公司 | A kind of handling process of antibiotic bacterium dregs |
| CN106925595A (en) * | 2015-12-30 | 2017-07-07 | 中粮营养健康研究院有限公司 | A kind of handling process of antibiotic bacterium dregs |
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| CN106925596B (en) * | 2015-12-30 | 2020-04-17 | 中粮营养健康研究院有限公司 | Treatment process of antibiotic fungi residues |
| CN106925595B (en) * | 2015-12-30 | 2020-04-17 | 中粮营养健康研究院有限公司 | Treatment process of antibiotic fungi residues |
| CN105924271A (en) * | 2016-04-22 | 2016-09-07 | 潘峰 | Biological organic fertilizer produced by using erythromycin bacterium residues and preparation method of biological organic fertilizer |
| CN107311729A (en) * | 2017-08-04 | 2017-11-03 | 哈尔滨工业大学 | A kind of method that utilization lincomycin fungi residues produce organic fertilizer |
| CN107324905A (en) * | 2017-08-04 | 2017-11-07 | 哈尔滨工业大学 | A kind of method that utilization erythromycin bacterium slag produces organic fertilizer |
| CN107353114A (en) * | 2017-08-09 | 2017-11-17 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using tetracycline antibiotics bacteria residue |
| CN107337496A (en) * | 2017-08-09 | 2017-11-10 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using tylosin dreg |
| CN107382419A (en) * | 2017-08-11 | 2017-11-24 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using macrolide antibiotic bacterium dregs |
| CN107337497A (en) * | 2017-08-11 | 2017-11-10 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using aminoglycoside antibiotics bacteria residue |
| CN107522546A (en) * | 2017-08-30 | 2017-12-29 | 哈尔滨工业大学 | A kind of method that organic fertilizer is produced using polypeptide antibiotics bacteria residue |
| CN107500984A (en) * | 2017-09-21 | 2017-12-22 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using Fenton process processing antibiotic bacterium dregs |
| CN107522525A (en) * | 2017-09-21 | 2017-12-29 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using ozone processing antibiotic bacterium dregs |
| CN109776238A (en) * | 2019-03-29 | 2019-05-21 | 山东睿智医药科技有限公司 | A method of functional organic fertilizer is produced using cephalosporin filter residue |
| CN110951637A (en) * | 2019-11-28 | 2020-04-03 | 宁夏泰益欣生物科技有限公司 | Novel method for treating erythrocin fungi residues |
| CN111440022A (en) * | 2020-03-17 | 2020-07-24 | 同济大学 | Preparation method and application of multi-element composite water-soluble fertilizer solid powder by using antibiotic fungi residues |
| CN112337033A (en) * | 2020-11-24 | 2021-02-09 | 内蒙古科技大学 | Harmless treatment method of abamectin slag, product and application of product as sandy soil modifier |
| CN114573379A (en) * | 2022-03-22 | 2022-06-03 | 丽珠集团福州福兴医药有限公司 | Method for fertilizing antibiotic mushroom dregs and organic fertilizer |
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