CN104108842A - External chemical-polluted bird guano treatment method - Google Patents
External chemical-polluted bird guano treatment method Download PDFInfo
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- CN104108842A CN104108842A CN201410225368.8A CN201410225368A CN104108842A CN 104108842 A CN104108842 A CN 104108842A CN 201410225368 A CN201410225368 A CN 201410225368A CN 104108842 A CN104108842 A CN 104108842A
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Abstract
The invention discloses an external chemical-polluted bird guano treatment method. The external chemical-polluted bird guano treatment method comprises the following steps of 1, material mixing treatment: mixing external chemical-polluted bird guano having water content of 50-60% and a treatment agent according to a mass ratio of 10: 1 to 5: 1 to obtain a uniform mixed material, wherein the treatment agent comprises Fe and/or a Fe-containing compound, and 2, stacking the mixed material obtained by the step 1 and a microwave-sensitized material in a way that the microwave-sensitized material layers are arranged in the stacked material at intervals of 5-8cm, and carrying out microwave treatment to obtain purified bird guano at microwave power of 1-2kW for 15-20min. The external chemical-polluted bird guano treatment method is safe, environmentally friendly, fast and stable and has simple processes, a high automation degree and a low cost.
Description
Technical field
The invention belongs to livestock waste process field, more specifically, relate to a kind for the treatment of process of exogenous chemicals pollution brid guano.
Background technology
Since the eighties in 20th century, livestock and poultry breeding industry, particularly intensive, batch production, large-scale cultivation develop rapidly.Along with intensive, the large quantities of of industrialized culture field emerge in large numbers, and have produced a large amount of feces of livestock and poultry and have piled up.According to China's statistic data of 2003, China's large-scale cultivation field feces of livestock and poultry generation reaches 1,713 hundred million tons, is 217 times of industrial solid wastes.In order to promote the growth of animal, improve Production of Livestock and Poultry efficiency, a large amount of feeding antibiotics and organic Arsiness are used as fodder additives and are widely used.Tetracycline antibiotics Ye Shi China is used maximum feeding antibiotics, data shows, China has reached 10000t the oxytetracycline single output of 2003, and 65%, the 2008 year tetracycline antibiotics medicine that accounts for world's terramycin production only export volume just reaches 1.34 × 10
7kg.From China's arsenic compound that begins one's study eighties in 20th century, within 1993, setting it as Drug additive uses, at present, organic arsine product that domestic production is used is mainly arsanilic acid and sodium salt (Pro-gen 90) and 3-nitro-4-hydroxybenzene arsenic acid (roxarsone).Raise a broiler chicken mean consumption roxarsone and be about 150mg, China delivers approximately 8,000,000,000 broiler chicken every year for sale, and roxarsone and metabolite thereof that feeding of broiler industry is discharged in environment are every year about 1000t, add pig industry, and quantity discharged is higher.Livestock and poultry can not absorb forage component, particularly bird completely, and owing to not having, teeth chewing and digestive tube are short, and food residence time in intestines is short, low to the digestibility of feed, approximately have 60%～90% nutritive ingredient not to be absorbed and to excrete with ight soil.Remain in the generation that microbiotic original shape in feces of livestock and poultry can cause drug resistant gene, and then the treatment that the mankind are caught an illness and micro-ecological environment form potential threat.Arsenic belongs to Class A carinogenicity chemical substance, and arsenic 70%～90% residual in ight soil is water miscible, once enter soil, penetrate in underground water, utmost point refractory reason and recovering, thus cause persistent pollution, and bring long-term carcinogenic risk.Therefore, control in the ight soil of poultry-farm the pollution of feeding antibiotic and organic Arsiness very urgent comprehensively.
Exogenous chemicals in brid guano refers to the chemical artificially adding for preventing and treating Animal diseases, promotion growth of animal etc. in breeding process, and microbiotic and organoarsenics are the large class exogenous chemical product of aquaculture topmost two.Because various exogenous pollution properties in brid guano are different, degradation treatment mode is also not quite similar.Existing is generally a kind of or a class exogenous pollution thing to the research object of feces of livestock and poultry treatment process, and has no the research report of simultaneously processing two class exogenous pollution things in ight soil.
Mostly China is to rest in detection analysis in the research of the residual antibiotics material of feces of livestock and poultry at present, and the report of studying its degraded and removal is also few, and technical is mainly biological degradation compost.And microbiotic itself just plays inhibition and killing action to bacterium and other microorganisms, also must suppress the Growth and Reproduction of anaerobion and aerobic microbiological in composting process, although therefore traditional biological treatment can be removed part microbiotic by biological degradation, act on limited.
At present, in ight soil, the research of organic arsine residue degrading is mainly the object that reaches the organic arsine body of degraded by biological degradation, photodegradation and thermal destruction, and harm research and the treatment technology of its degraded product are not appeared in the newspapers.But the organic arsine itself of degrading does not reduce the total arsenic content in ight soil, arsenic is present in the degraded product of organic arsine with arsenate and other forms, these inorganic arsenics have the environmental ecology toxicity more much bigger than organic arsine and very strong water-soluble and mobility, be delivered to the mankind with food chain, human body is produced to potential serious harm.
Need at present a kind of safety and environmental protection, fast and stable, technical process is simple, and level of automation is high, lower-cost integrated conduct method.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides the treatment process that a kind of exogenous chemicals pollutes brid guano, its object is by microwave treatment technology and heavy metal stabilization technical tie-up, thereby process efficiently containing microbiotic and organic arsine brid guano simultaneously, solve thus current treatment process and can not comprehensively solve the xenobiotic pollutants such as microbiotic and organic arsine, simultaneously the not good technical problem for the treatment of effect.
For achieving the above object, according to one aspect of the present invention, provide a kind of exogenous chemicals to pollute the treatment process of brid guano, it is characterized in that, comprised the following steps:
(1) combination treatment material: brid guano and treatment agent that the exogenous chemicals by water ratio between 50% to 60% pollutes, according to mass ratio, 10:1 to 5:1 evenly mixes, and obtains mixture; Described treatment agent is iron and/or iron containing compounds;
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), alternating floor microwave sensitized material between described mixture every 5 to 8cm, carries out microwave treatment, obtains the brid guano purifying; Microwave power between 1kW to 2kW, 15 to 20 minutes microwave time.
Preferably, described treatment process, the described iron containing compounds of its step (1) is ferrous sulfate and hydrate thereof, FeCl
2, FeCl
3, Fe (NO
3)
3, Fe
3o
4and/or Fe
2o
3.
Preferably, described treatment process, the described microwave sensitized material of its step (2) is the matrix material of silicon carbide, graphite or silicon carbide-containing and graphite.
Preferably, described treatment process, described in it, brid guano is chicken manure, duck excrement, goose excrement and/or pigeon dung.
In general, the above technical scheme of conceiving by the present invention compared with prior art, can obtain following beneficial effect:
(1) adopt iron or iron containing compounds as treatment agent, all there is larger dielectric loss factor, also just have stronger wave-sucking performance, under microwave condition, FeSO
47H
2o, FeCl
2, FeCl
3, Fe (NO
3)
3also all there is stronger microwave sensibilized Deng the ferric oxide and the dewatered product that decompose generation, therefore just strengthened the Degradation of microwave to antibiotic decomposition and organic arsine adding of these iron series compounds.
(2) treatment agent that the present invention adds can effectively be consolidated arsenic, iron ion belongs to light current ion, run into the moisture in brid guano, hydrolysis just occurs brid guano system is become under solutions of weak acidity (pH5-6), in the process stirring, generate stable ferric arsenate precipitation with arsenate.Alkalescence too conference makes iron and iron containing compounds generate ironic hydroxide, is difficult to generate precipitation with arsenate combination; And the excessive arsenate ion that easily makes of acidity generates the forms such as arsenic acid hydrogen radical ion, increase the solubleness of ferric arsenate.Therefore the add-on for the treatment of agent of the present invention has material impact to the stabilising effect of arsenic.
(3) having effectively utilized solid arsenic effect and the iron that High Efficiency Thermal effect, non-thermal effect and the iron of microwave radiation and iron containing compounds are good is the strong microwave sensibilized of material, utilize microwave technology, for example burn pollution-free generation than compost and other technologies, there is safe, convenient, environmental protection.
(4) can remove microbiotic and organic arsine in brid guano simultaneously, and complete stabilization, the immobilization processing to inorganic arsenic simultaneously.Method of the present invention can reach 85-99% to antibiotic clearance, the leaching concentration decline 90-99% of arsenic.
(5) exogenous chemicals provided by the invention pollutes the treatment process of brid guano, and whole technical process is simple, be easy to realize, and level of automation is high, is convenient to industrial applications.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
Microwave radiation can be accelerated chemical reaction rate and reduce reaction activity, accelerate chemical reaction rate, and electromagnetic field can also cause the non-thermal effects such as electrical effect, magnetic effect and chemical effect to the direct effect of intermolecular behavior, effectively promote antibiotic oxidative degradation, microwave has obvious fixed action to heavy metal simultaneously.FeSO
47H
2o, FeCl
2, FeCl
3, Fe (NO
3)
3deng, can enlarge markedly the specific inductivity of material, also just improve the absorptive character of microwave, under the heat effect of microwave, decomposite red iron oxide (Fe
2o
3) and its dewatered product, and ferric oxide and its dewatered product all have the ability that strengthens absorbing property.Adding under the condition of microwave absorption, microwave action can make rapidly material handling reach very high temperature, thereby thoroughly realizes organic degraded fast, simultaneously FeSO
47H
2the iron such as O are the stablizer containing arsenic solid waste that thing is still commonly used.
Exogenous chemicals provided by the invention pollutes the treatment process of brid guano, comprises the following steps:
(1) combination treatment material: brid guano and treatment agent that the exogenous chemicals by water ratio between 50% to 60% pollutes, according to mass ratio, 10:1 to 5:1 evenly mixes, and obtains mixture; Described treatment agent is iron and/or iron containing compounds; Described iron containing compounds is ferrous sulfate and hydrate thereof, FeCl
2, FeCl
3, Fe (NO
3)
3, Fe
3o
4and/or Fe
2o
3.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), alternating floor microwave sensitized material between described mixture every 5 to 8cm, carries out microwave treatment, obtains the brid guano purifying; Tiling thickness between 5cm to 8cm, microwave power between 1kW to 2kW, 15 to 20 minutes microwave time.Described microwave sensitized material is the matrix material of silicon carbide, graphite or silicon carbide-containing and graphite.
External source product provided by the invention pollute the treatment process of brid guano, are applicable to various pure brid guanos or rice bed and cultivate the brid guano with paddy.Described brid guano includes but not limited to chicken manure, duck excrement, goose excrement and/or pigeon dung.
Be below embodiment:
Embodiment 1
Exogenous chemicals pollutes a treatment process for pure or chicken manure, duck excrement, goose excrement and/or pigeon dung with paddy, comprises the following steps:
(1) combination treatment material: chicken manure and treatment agent that the exogenous chemicals that is 50% by water ratio pollutes, according to mass ratio, 10:1 evenly mixes, and obtains mixture; Described treatment agent is FeSO
47H
2o.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), between the every 5cm of described mixture, alternating floor microwave sensitized material, carries out microwave treatment, obtains the chicken manure purifying; Microwave power is 1kW, 15 minutes microwave time.Described microwave sensitized material is silicon carbide.
Embodiment 2
Exogenous chemicals pollutes a treatment process for pure or chicken manure, duck excrement, goose excrement and/or pigeon dung with paddy, comprises the following steps:
(1) combination treatment material: duck excrement and treatment agent that the exogenous chemicals that is 55% by water ratio pollutes, according to mass ratio, 8:1 evenly mixes, and obtains mixture; Described treatment agent is FeCl
2.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), between the every 6cm of described mixture, alternating floor microwave sensitized material, carries out microwave treatment, obtains the duck excrement purifying; Microwave power is 1.5kW, 18 minutes microwave time.Described microwave sensitized material is graphite.
Embodiment 3
Exogenous chemicals pollutes a treatment process for pure or chicken manure, duck excrement, goose excrement and/or pigeon dung with paddy, comprises the following steps:
(1) combination treatment material: goose excrement and treatment agent that the exogenous chemicals that is 60% by water ratio pollutes, according to mass ratio, 6:1 evenly mixes, and obtains mixture; Described treatment agent is Fe (NO
3)
3.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), between the every 7cm of described mixture, alternating floor microwave sensitized material, carries out microwave treatment, obtains the goose excrement purifying; Microwave power is 1.8kW, 18 minutes microwave time.The matrix material that described microwave sensitized material is silicon carbide-graphite.
Embodiment 4
Exogenous chemicals pollutes a treatment process for pure or chicken manure, duck excrement, goose excrement and/or pigeon dung with paddy, comprises the following steps:
(1) combination treatment material: pigeon dung and treatment agent that the exogenous chemicals that is 60% by water ratio pollutes, according to mass ratio, 5:1 evenly mixes, and obtains mixture; Described treatment agent is Fe
3o
4.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), between the every 8cm of described mixture, alternating floor microwave sensitized material, carries out microwave treatment, obtains the pigeon dung purifying; Microwave power is 2kW, 20 minutes microwave time.The matrix material that described microwave sensitized material is silicon carbide-graphite.
Embodiment 5
Embodiment 1 to embodiment 4 tsiklomitsin and terramycin degradation effect are measured:
Brid guano before and after treatment in embodiment 1 to 4 is measured to tsiklomitsin, terramycin content with high performance liquid chromatography (HPLC) respectively after extraction, Solid phase extraction.
Instrument comprises: high performance liquid chromatograph (Agilent1200, USA), and configuration: G1310A modular pump, G1314B UV-detector, Instrument chem workstation, sampling valve quantitatively encircles with 20 μ L.
HPLC condition: chromatographic column: Agilent Eclipse XDB-C18 (5 μ m, 4.6 × 150mm); Flow velocity: 0.8ml/min; Sample size 20 μ L; Moving phase: acetonitrile-methyl alcohol-0.01mol/L oxalic acid solution (18:5:77, V/V); Detect wavelength: 350nm; Column temperature: room temperature.
Measure embodiment 1 to 4 tsiklomitsin and the terramycin content in brid guano before and after treatment, in table 1.The degradation rate of calculating embodiment 1 to 4 treatment process, degradation rate is the per-cent that the antibiotic concentration of the front brid guano of processing and the difference of processing the antibiotic concentration of rear brid guano account for the antibiotic concentration of the front brid guano of processing.As shown in Table 1, in embodiment 1 to 4, the degradation rate of tsiklomitsin and terramycin all reaches more than 90%, and present method has good microbiotic decontamination effect improving.
Table 1 embodiment 1 to 4 is tsiklomitsin and the terramycin content in brid guano before and after treatment
Embodiment 6
Embodiment 1 to embodiment 4 arsenic Leaching is measured:
Brid guano before and after treatment in embodiment 1 to embodiment 4 after leaching, sulfuric acid nitrate method is measured to leaching arsenic concentration with Atomic Fluorescence Spectroscopy (AFS) (AFS9600, Beijing Kechuang Haiguang Instrument Co., Ltd).Atomic fluorescence condition: photomultiplier negative high voltage: 300V; High-strength hollow cathode fluorescent lamp electric current: 60mA; Carrier gas flux: 300mL/min; Shield gas flow amount: 800mL/min; Atomizer height: 8mm.
Measure embodiment 1 to the 4 arsenic leaching concentration of brid guano before and after treatment, in table 2.Steadyization/curing degree of calculating embodiment 1 to 4, steadyization/curing degree is the per-cent that the arsenic leaching concentration of the front brid guano of processing and the difference of processing the arsenic leaching concentration of rear brid guano account for the arsenic leaching concentration of the front brid guano of processing.As shown in Table 2, in embodiment 1 to 4, the steadyization curing degree of arsenic all, more than 90%, illustrates that present method has good steadyization/solidification effect to heavy metal arsenic.
The arsenic leaching concentration of brid guano before and after treatment in table 2 embodiment 1 to embodiment 4
| Embodiment | Before processing (mg/L) | After processing (mg/L) | Steadyization/curing degree (%) |
| 1 | 4.80 | 0.13 | 97.1 |
| 2 | 4.83 | 0.08 | 98.3 |
| 3 | 4.88 | 0.005 | 99.9 |
| 4 | 4.82 | 0.46 | 90.5 |
Embodiment 7
The treatment effect comparison for the treatment of agent:
According to following steps, process chicken manure respectively:
(1) combination treatment material: chicken manure and treatment agent that the exogenous chemicals that is 55% by water ratio pollutes, evenly mix according to mass ratio 8:1 respectively, obtain mixture; Described treatment agent is respectively Fe, FeSO
47H
2o, FeCl
2, FeCl
3, Fe (NO
3)
3, Fe
3o
4and Fe
2o
3.
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), between the every 8cm of described mixture, alternating floor microwave sensitized material, carries out microwave treatment, obtains the chicken manure purifying; Microwave power is 2kW, 15 minutes microwave time.The matrix material that described microwave sensitized material is silicon carbide-graphite.
According to the method in embodiment 5 and embodiment 6, measure respectively Fe, FeSO
47H
2o, FeCl
2, FeCl
3, Fe (NO
3)
3, Fe
3o
4and Fe
2o
3processing rate (being the degradation rate of terramycin and tsiklomitsin, the steadyization/curing degree of arsenic), as shown in table 3.
The effect comparison of the various treatment agents of table 3
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. exogenous chemicals pollutes a treatment process for brid guano, it is characterized in that, comprises the following steps:
(1) combination treatment material: brid guano and treatment agent that the exogenous chemicals by water ratio between 50% to 60% pollutes, according to mass ratio, 10:1 to 5:1 evenly mixes, and obtains mixture; Described treatment agent is iron and/or iron containing compounds;
(2) by stacking to the mixture and the microwave sensitized material that obtain in step (1), alternating floor microwave sensitized material between described mixture every 5 to 8cm, carries out microwave treatment, obtains the brid guano purifying; Microwave power between 1kW to 2kW, 15 to 20 minutes microwave time.
2. treatment process as claimed in claim 1, is characterized in that, the described iron containing compounds of step (1) is ferrous sulfate and hydrate thereof, FeCl
2, FeCl
3, Fe (NO
3)
3, Fe
3o
4and/or Fe
2o
3.
3. treatment process as claimed in claim 1, is characterized in that, the described microwave sensitized material of step (2) is the matrix material of silicon carbide, graphite or silicon carbide-containing and graphite.
4. treatment process as claimed in claim 1, is characterized in that, described brid guano is chicken manure, duck excrement, goose excrement and/or pigeon dung.
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Cited By (4)
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| CN107162708A (en) * | 2017-04-21 | 2017-09-15 | 华中科技大学 | A kind of method that ecological organic coarse fertilizer is prepared by fast degradation animal waste |
| CN108704239A (en) * | 2018-07-26 | 2018-10-26 | 华中科技大学 | A kind of realgar tailings slag stabilization treatment method |
| CN114634220A (en) * | 2022-01-18 | 2022-06-17 | 华东理工大学 | Method for photodegrading organic arsenide |
| TWI841517B (en) * | 2024-01-11 | 2024-05-01 | 鼎盛興農業科技股份有限公司 | Method for producing poultry excrement conversion agent |
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| CN103319060A (en) * | 2013-06-17 | 2013-09-25 | 长江水利委员会长江科学院 | Microwave induced catalytic oxidation immobilization treatment method for arsenic in sediments |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162708A (en) * | 2017-04-21 | 2017-09-15 | 华中科技大学 | A kind of method that ecological organic coarse fertilizer is prepared by fast degradation animal waste |
| CN108704239A (en) * | 2018-07-26 | 2018-10-26 | 华中科技大学 | A kind of realgar tailings slag stabilization treatment method |
| CN108704239B (en) * | 2018-07-26 | 2020-05-19 | 华中科技大学 | Realgar tailing slag stabilization treatment method |
| CN114634220A (en) * | 2022-01-18 | 2022-06-17 | 华东理工大学 | Method for photodegrading organic arsenide |
| TWI841517B (en) * | 2024-01-11 | 2024-05-01 | 鼎盛興農業科技股份有限公司 | Method for producing poultry excrement conversion agent |
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|---|---|
| CN104108842B (en) | 2015-09-23 |
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