CN103145212A - Method for treating tetracycline-containing wastewater - Google Patents

Abstract

The invention provides a method for treating tetracycline-containing wastewater. The method comprises the step of treating the tetracycline-containing wastewater by adopting ionizing radiation. The method has the advantages of short treatment time, high removal rate, easiness in operation and no secondary pollution.

Description

The treatment process that contains tetracycline wastewater

Technical field

The present invention relates to a kind for the treatment of process that contains tetracycline wastewater, particularly a kind of method of utilizing the ionizing radiation technology to process containing tetracycline wastewater.

Background technology

Tetracycline antibiotics is a class Broad spectrum antibiotics that is produced by streptomycete; all microbiotic of sensitivity of a kind of Gram-negative and gram positive bacterium; the derivative that belongs to many ring tetracene Carboxylamide parent nucleus on chemical structure; can be divided into natural product and tetracycline antibiotics; generally by being combined with ribosomal 30S subunit; prevention aminoacyl tRNA in conjunction with producing pharmacological action, plays antibacterial, germicidal action with ribosome.

Along with developing rapidly of intensive modern livestock and poultry breeding industry, tetracycline medication makes tetracycline medication be in the state of being abused for a long time because its inhibition or killing action to various pathogenic micro-organism brute forces is widely used in animal husbandry and aquaculture.Yet, tetracycline medication can not be absorbed by animal fully, but there is considerable part to enter in environment with ight soil and urine with the form of original shape or metabolite, tetracycline medication has the characteristics of good water solubility, left drug very easily enters surperficial water body, and various sewage treatment process to the tetracycline medication in sewage inoperative or the effect seldom, so left drug finally is discharged in water surrounding.Tetracycline medication has the existence of different concns in water surrounding, these medicines produce extensively and far-reaching influence environmental organism and ecology as the environment exogenous chemical, and final health and living environment generation adverse influence to the mankind, sustainable existence such as tetracycline medication in water surrounding, will select or induce the water body drug-resistant bacteria to the water body bacterium, so in environment, residual tetracycline antibiotics is huge to the harm of environmental ecology and the threat of human health.The pollution of tetracycline antibiotics is a global ubiquitous problem, and no matter in the consumption of medical or tetracycline antibiotics for animals, China is even more serious than other countries, in the environment that thereupon causes the pollution problem of tetracycline medication is also apparent, so the removal problem of this pollutant can not be ignored.

At present, sewage work when processing hospital wastewater and sanitary sewage, is generally all Technology development and the technique that adopts, and can't thoroughly remove the tetracycline antibiotics in water.And the method for processing tetracycline wastewater both at home and abroad mainly contains biochemical process, absorption method and photocatalytic oxidation etc.Studies show that, all there is certain limitation in above-mentioned treatment process.Because tsiklomitsin can suppress the protein synthesis of microorganism as broad-spectrum antibiotics, so the most of microbe in biochemical treatment waste water process all is subject to obvious restraining effect, thereby affected treatment effect; In absorption method, loading capacity is low, and sorbent material recovery processing is cumbersome, and processing cost is high; In photocatalytic oxidation, the restriction of reaction unit makes the method be only applicable to the processing of tetracycline wastewater on a small scale.Therefore, provide a new processing tetracycline wastewater method, just becoming the focus of domestic and international research.

Summary of the invention

For problems of the prior art, one object of the present invention is to provide the treatment process that contains tetracycline wastewater, and this disposal methods time is short, clearance is high, easy handling, non-secondary pollution.

For achieving the above object, the invention provides a kind for the treatment of process that contains tetracycline wastewater, comprise that adopting ionizing radiation to process contains tetracycline wastewater, decomposes tsiklomitsin.

According to an embodiment of the invention, described ionizing radiation comprises alpha irradiation, β irradiation, γ irradiation and neutron irradiation.

According to another implementation of the invention, described γ irradiation comprises electron beam irradiation and radio isotope irradiation.

According to another implementation of the invention, described radio isotope comprises Cs-137 and Co-60.

According to another implementation of the invention, the irradiation dose of described ionizing radiation is below 13kGy.

According to another implementation of the invention, the irradiation dose of described ionizing radiation is 4kGy, 6kGy, 10kGy or 13kGy.

According to another implementation of the invention, the described concentration that contains tsiklomitsin in tetracycline wastewater is 1-100ppm.

According to another implementation of the invention, describedly contain that in tetracycline wastewater, tsiklomitsin concentration is 1ppm, 5ppm, 10ppm, 20ppm or 100ppm.

According to another implementation of the invention, during less than 4kGy, tsiklomitsin rate of decomposition and described irradiation dose are linear when described irradiation dose, and the coefficient R value is 0.99, wherein

$R=\frac{\mathrm{\Σ}(X_i-\stackrel{\‾}{X})(Y_i-\stackrel{\‾}{Y})}{\sqrt{\mathrm{\Σ}{(X_i-\stackrel{\‾}{X})}^2\sqrt{\mathrm{\Σ}{(Y_i-\stackrel{\‾}{Y})}^2}}},$

In formula, X is irradiation dose, and Y is the tsiklomitsin rate of decomposition.

The electron irradiation that the treatment process that contains tetracycline wastewater provided by the invention is utilized is being brought into play more and more important effect as a kind of technology that application prospect is arranged very much in wastewater treatment.The present invention decomposes the irradiation of tsiklomitsin in waste water and has carried out systematic research, finds the fast and effeciently tsiklomitsin in Decomposition Wastewater of electron irradiation.Obtaining as electron irradiation application aspect the tsiklomitsin removal in waste water lays a solid foundation of these achievements, the advantages such as electron irradiation is effective and rapid with it, penetrativity strong, the additional toxicity of nothing, noresidue harm are applied widely aspect wastewater treatment.

Description of drawings

Fig. 1 is tsiklomitsin rate of decomposition and the irradiation dose graph of a relation that contains tetracycline wastewater in the embodiment of the present invention 6;

Fig. 2 is that in the embodiment of the present invention 6, irradiation dose is mass spectrum after the processing that contains tetracycline wastewater of 3.2kGy.

Embodiment

The invention will be further described below in conjunction with drawings and Examples.But the present invention is not limited to following embodiment.

Embodiment 1

Choose four parts and contain tetracycline wastewater, tsiklomitsin concentration is 1ppm, use rumbatron (10MeV/15kW S-band stationary wave electron linear irradiation accelerator, Institute of High Energy Physcis, Academia Sinica's manufacturing) produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, irradiation dose is respectively 4kGy, 6kGy, 10kGy and 13kGy.Solution after irradiation is analyzed (U.S. Waters company high performance liquid chromatograph, 5 μ m, 4.6mm * 250mm HYPERSIL BDS C18 reversed-phase liquid chromatography post) with HPLC, obtains tsiklomitsin rate of decomposition in processed waste water, and the data obtained sees Table 1.

Embodiment 2

Choose four parts and contain tetracycline wastewater, tsiklomitsin concentration is 5ppm, uses rumbatron to produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, and irradiation dose is respectively 4kGy, 6kGy, 10kGy and 13kGy.Solution after irradiation is analyzed with HPLC, obtains tsiklomitsin rate of decomposition in processed waste water, and the data obtained sees Table 1.

Embodiment 3

Choose four parts and contain tetracycline wastewater, tsiklomitsin concentration is 10ppm, uses rumbatron to produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, and irradiation dose is respectively 4kGy, 6kGy, 10kGy and 13kGy.Solution after irradiation is analyzed with HPLC, obtains tsiklomitsin rate of decomposition in processed waste water, and the data obtained sees Table 1.

Embodiment 4

Choose four parts and contain tetracycline wastewater, tsiklomitsin concentration is 20ppm, uses rumbatron to produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, and irradiation dose is respectively 4kGy, 6kGy, 10kGy and 13kGy.Solution after irradiation is analyzed with HPLC, obtains tsiklomitsin rate of decomposition in processed waste water, and the data obtained sees Table 1.

Embodiment 5

Choose four parts and contain tetracycline wastewater, tsiklomitsin concentration is 100ppm, uses rumbatron to produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, and irradiation dose is respectively 4kGy, 6kGy, 10kGy and 13kGy.Solution after irradiation is analyzed with HPLC, obtains tsiklomitsin rate of decomposition in processed waste water, and the data obtained sees Table 1.

Contain tsiklomitsin rate of decomposition (%) in tetracycline wastewater under the different radiation parameters of table 1.

?	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						Irradiation dose	Concentration 1ppm	Concentration 5ppm	Concentration 10ppm	Concentration 20ppm	Concentration 100ppm
4kGy	100.0	100.0	99.2	99.4	97.1
						6kGy	100.0	100.0	100.0	99.4	98.4
10kGy	100.0	100.0	100.0	99.9	99.5
						13kGy	100.0	100.0	100.0	100.0	99.7

By as seen from Table 1, electron irradiation is the tsiklomitsin in water of decomposition effectively, and the concentration height correlation of tsiklomitsin in the rate of decomposition of tsiklomitsin and irradiation dose and water body, under the irradiation dose of 13kGy, can be with the tsiklomitsin full scale clearance of low concentration in water body, reached 99.7% up to the tsiklomitsin rate of decomposition of 100ppm concentration.Thus, we can determine, electronic irradiation technique not only can effectively be processed lower concentration and contain tetracycline wastewater, and can effectively process high density and contain tetracycline wastewater.

Embodiment 6

Choose five parts and contain tetracycline wastewater, tsiklomitsin concentration is 20ppm, uses rumbatron to produce electron beam the selected tetracycline wastewater that contains is carried out irradiation, and irradiation dose is respectively 1.4kGy, 1.6kGy, 2.8kGy, 3.0kGy and 3.2kGy.Solution after irradiation is analyzed with HPLC, obtains that in processed waste water, tsiklomitsin decomposition situation is respectively: when irradiation dose was 1.4kGy, about 65% tsiklomitsin was decomposed; When irradiation dose was 1.6kGy, about 69% tsiklomitsin was decomposed; When irradiation dose was 2.8kGy, about 88% tsiklomitsin was decomposed; When irradiation dose was 3.0kGy, about 93% tsiklomitsin was decomposed; When irradiation dose was 3.2kGy, about 96% tsiklomitsin was decomposed.As shown in Figure 1, tsiklomitsin rate of decomposition and irradiation dose are linear, and trying to achieve the coefficient R value is 0.99, wherein

$R=\frac{\mathrm{\Σ}(X_i-\stackrel{\‾}{X})(Y_i-\stackrel{\‾}{Y})}{\sqrt{\mathrm{\Σ}{(X_i-\stackrel{\‾}{X})}^2\sqrt{\mathrm{\Σ}{(Y_i-\stackrel{\‾}{Y})}^2}}},$

In formula, X is irradiation dose, and Y is the tsiklomitsin rate of decomposition.

The tetracycline wastewater sample that contains that is 3.2kGy with irradiation dose is dissolved in and carries out Electrospray Ionization Mass Spectrometry (1200 liquid chromatographies of Agilent Technologies company/linear ion hydrazine mass spectrometry Agilent1200/6340 of system) in 80% methanol/water, acquired results as shown in Figure 2, the molecular ion peak that tsiklomitsin is corresponding should be the m/z445.3 ion, do not observe the m/z445.3 ion in the mass spectrum experimentation, but observed the tsiklomitsin molecule add sodium peak [M+Na]+, i.e. m/z468.5 ion.Be no matter the tsiklomitsin molecular ion peak or add the sodium peak, its intensity is compared all with pre-irradiation and is greatly weakened, and shows that most tsiklomitsin molecule is decomposed by electron beam irradiation.Equally, in the lower molecular weight zone, some new molecular ion peaks have appearred, the different decomposition product that these mass spectra peaks also produce after corresponding electron beam irradiation.Therefore confirmable is that through the irradiation of electron beam short period of time, tsiklomitsin has been effectively decomposed.

Various embodiments of the present invention all adopt rumbatron (10MeV/15kW S-band stationary wave electron linear irradiation accelerator, Institute of High Energy Physcis, Academia Sinica's manufacturing) mode that produces electron beam is carried out irradiation, but ionizing radiation is processed and is comprised alpha irradiation, β irradiation, γ irradiation and neutron irradiation, also specifically comprises electron beam irradiation and radio isotope irradiation (radio isotope comprises Cs-137 and Co-60) in γ irradiation.

These ionizing radiation modes all can be applicable in the present invention, because various ionizing radiations application principle in the present invention are identical, all that irradiation energy is transferred to by irradiated material, make by irradiated material and produce ionization and excite, discharge orbital electron, form free radical, control radiation condition, make and changed by the physicals of irradiated material and chemical constitution and can make it become the needed a kind of new material of people, or make organism (microorganism etc.) be subject to expendable loss and destruction, reach the needed target of people.In the present invention, contain tetracycline wastewater by irradiation after, water molecules can generate a series of radiolysis products with very strong activity, as-OH ,-H, H ₂O ₂Deng, the tetracyclines pollutent is decomposed, reach emission standard.

Single with regard to the tsiklomitsin removal effect, such as biochemical process, absorption method and photocatalytic oxidation etc. in prior art, when the processing lower concentration contains tetracycline wastewater (below 20ppm), clearance can only reach 99% at most, and when processing high density and containing tetracycline wastewater (more than 20ppm), clearance is less than 90% often, by comparison, referring to data in above-mentioned table 1, the effect that contains the treatment process of tetracycline wastewater provided by the invention is much better than prior art.

Above-described; it is only preferred embodiment of the present invention; be not to limit scope of the present invention, i.e. every simple, equivalence of doing according to claims and the description of the present patent application changes and modifies, and all falls into the claim protection domain of patent of the present invention.

Claims (9)

1. a treatment process that contains tetracycline wastewater, the treating method comprises and adopt the ionizing radiation processing to contain tetracycline wastewater, and tsiklomitsin is decomposed.

2. the treatment process that contains tetracycline wastewater according to claim 1, wherein said ionizing radiation comprises alpha irradiation, β irradiation, γ irradiation and neutron irradiation.

3. the treatment process that contains tetracycline wastewater according to claim 2, wherein said γ irradiation comprises electron beam irradiation and radio isotope irradiation.

4. the treatment process that contains tetracycline wastewater according to claim 3, wherein said radio isotope comprises Cs-137 and Co-60.

5. the described treatment process that contains tetracycline wastewater of any one according to claim 1 to 4, the irradiation dose of wherein said ionizing radiation is below 13kGy.

6. the treatment process that contains tetracycline wastewater according to claim 5, the irradiation dose of wherein said ionizing radiation is 4kGy, 6kGy, 10kGy or 13kGy.

7. the treatment process that contains tetracycline wastewater according to claim 6, the wherein said concentration that contains tsiklomitsin in tetracycline wastewater is 1-100ppm.

8. the treatment process that contains tetracycline wastewater according to claim 7 wherein saidly contains that in tetracycline wastewater, tsiklomitsin concentration is 1ppm, 5ppm, 10ppm, 20ppm or 100ppm.

9. the treatment process that contains tetracycline wastewater according to claim 5, wherein when described irradiation dose during less than 4kGy, tsiklomitsin rate of decomposition and described irradiation dose are linear, and the coefficient R value is 0.99, wherein

$R=\frac{\mathrm{\Σ}(X_i-\stackrel{\‾}{X})(Y_i-\stackrel{\‾}{Y})}{\sqrt{\mathrm{\Σ}{(X_i-\stackrel{\‾}{X})}^2\sqrt{\mathrm{\Σ}{(Y_i-\stackrel{\‾}{Y})}^2}}},$

In formula, X is irradiation dose, and Y is the tsiklomitsin rate of decomposition.

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