CN105366759A - Degrading method for rhodamine B - Google Patents
Degrading method for rhodamine B Download PDFInfo
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- CN105366759A CN105366759A CN201510943836.XA CN201510943836A CN105366759A CN 105366759 A CN105366759 A CN 105366759A CN 201510943836 A CN201510943836 A CN 201510943836A CN 105366759 A CN105366759 A CN 105366759A
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- rhodamine
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/307—Treatment of water, waste water, or sewage by irradiation with X-rays or gamma radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention discloses a degrading method for rhodamine B. The method comprises the specific steps that a rhodamine B solid or solution sample is prepared; X-rays or gamma-rays are utilized for carrying out irradiation degrading on the rhodamine B sample. According to the method, the X-ray or gamma-ray irradiation technology is utilized for degrading a carcinogenic pollutant rhodamine B, the rhodamine B solid degrading rate is 12% or above, the rhodamine B solution degrading rate is 98% or above, the degrading effect is obvious, and cost is low; under the condition of the prior art, the irradiation process is controllable, the irradiation rays will not remain, secondary pollution to the environment is avoided, and the method has a good application prospect in the aspects of water pollution treatment and soil pollution treatment.
Description
Technical field
The invention belongs to nuisance degradation technique field, relate to the degradation method of a kind of rhodamine B.
Background technology
Irradiation technique is the effect utilized between ray and material, ionizes and excite activated atom and the activated molecule of generation, makes it and material generation series of physical, chemistry, biochemical change, causes the degraded of material, polymerization, be cross-linked and modification occurs.Conventional irradiation has gamma-radiation irradiation and X-x ray irradiation x.
Rhodamine B, English name is RhodamineB, CAS 81-88-9, it is a kind of industrial dye of synthetic, be used to the industries such as weaving, leather, woodwork, tinted shade, fireworks and firecrackers, it has carcinogenesis to human body, and improper use can cause environmental pollution, especially soil and water pollutions.
The Study on degradation of current rhodamine B, mainly in photocatalytic degradation field, utilizes the research of irradiation technique rhodamine B degradation to there is not yet pertinent literature report.Although irradiation ray is harmful, at present can specification, controlled use, and ray itself can not exist residual, can not cause uncontrollable harm.Irradiation technique obtains application in multiple field at present, but investigation and application is less in elimination bad environmental pollutent.
Summary of the invention
The object of this invention is to provide the degradation method of a kind of rhodamine B, the degraded for rhodamine B provides a kind of new method.
The technical solution adopted in the present invention is, the degradation method of a kind of rhodamine B, specifically implements according to the following steps: prepare rhodamine B solid or liquor sample; X-ray or gamma-radiation is utilized to carry out irradiation-induced degradation to rhodamine B sample.
Feature of the present invention is also,
The preparation of rhodamine B liquor sample, is specially: dissolved in ethanol by rhodamine B solid, then with ultrapure water dilution, obtains rhodamine B liquor sample.
The concentration of rhodamine B-ethanolic soln is 0.4 ~ 0.5mg/mL, and the concentration of the rhodamine B liquor sample after dilution is 0.16 ~ 0.2mg/mL.
In rhodamine B solid sample X-x ray irradiation x degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
In rhodamine B liquor sample X-x ray irradiation x degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
In rhodamine B solid sample gamma-radiation irradiation-induced degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
In rhodamine B liquor sample gamma-radiation irradiation-induced degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
The invention has the beneficial effects as follows, the present invention utilizes X-ray or gamma-radiation irradiation technique to degrade to carcinogenic contaminant rhodamine B, reaches more than 12%, reach more than 98% to the degradation rate of rhodamine B solution to the degradation rate of rhodamine B solid, degradation effect is fairly obvious, and with low cost.Under prior art conditions, irradiation process is controlled, and irradiation ray can not remain itself, can not cause secondary pollution to environment, in process water pollutions, soil pollution, have good application prospect.
Accompanying drawing explanation
Fig. 1 is the liquid chromatography comparison diagram after rhodamine B solid (being mixed with 1 μ g/mL) pre-irradiation;
Fig. 2 is the liquid chromatography comparison diagram after rhodamine B solution (being diluted to 1 μ g/mL) pre-irradiation;
Fig. 3 is rhodamine B solution pre-irradiation liquid chromatography-high resolution mass spectrum ion flow graph;
Fig. 4 is liquid chromatography after rhodamine B solution irradiation-high resolution mass spectrum ion flow graph;
Fig. 5 is rhodamine B high resolution mass spectrum scanning mass spectrum (1 μ g/mL);
Fig. 6 is rhodamine B radiolysis products 1 high resolution mass spectrum scanning mass spectrum;
Fig. 7 is rhodamine B radiolysis products 2 high resolution mass spectrum scanning mass spectrum.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The invention provides the degradation method of a kind of rhodamine B, specifically implement according to the following steps:
Step 1, sample prepares:
The preparation of solid sample: take about 80 ~ 100mg rhodamine B (purity >99%) and be loaded in 1.5mL transparent plastics centrifuge tube, to be irradiated.
The preparation of liquor sample: take appropriate rhodamine B, become concentration to be the solution of 0.4 ~ 0.5mg/mL with dissolve with ethanol, the amount of solution of preparation is no less than 50mL, get 40mL, be diluted to 100mL with ultrapure water, be mixed with the rhodamine B solution of 0.16 ~ 0.2mg/mL, sample solution is scarlet, to be irradiated.
Step 2, irradiation-induced degradation:
Utilize X-ray biological irradiation device to carry out irradiation to the rhodamine B sample that step 1 obtains, accumulative irradiation dose is 2.7 ~ 3.3kGy, namely completes the degraded of rhodamine B.
Or the gamma-radiation adopting cobalt-60 to produce carries out irradiation to the rhodamine B sample that step 1 obtains, and accumulative irradiation dose is 2.7 ~ 3.3kGy, namely completes the degraded of rhodamine B.
Embodiment 1
Step 1, sample prepares:
The preparation of solid sample: take 80mg rhodamine B (purity >99%) and be loaded in 1.5mL transparent plastics centrifuge tube, parallelly takes 3 parts, to be irradiated.
The preparation of liquor sample: take appropriate rhodamine B, concentration is become to be the solution of 0.4mg/mL with dissolve with ethanol, the amount of solution of preparation is no less than 50mL, get 40mL, be diluted to 100mL with ultrapure water, be mixed with the rhodamine B solution of 0.16mg/mL, be sub-packed in 3 20mL transparent plastic bottles, 10mL in each bottle, sample solution is scarlet, to be irradiated.
Step 2, irradiation-induced degradation:
Utilize X-ray biological irradiation device to carry out irradiation to the rhodamine B sample that step 1 obtains, accumulative irradiation dose is respectively 0.9kGy, 1.0kGy, 1.1kGy, and after irradiation, solid sample outward appearance is without considerable change, and liquor sample color shoals a little.
Embodiment 2
Step 1, sample prepares:
The preparation of solid sample: take 80mg rhodamine B (purity >99%) and be loaded in 1.5mL transparent plastics centrifuge tube, parallelly takes 2 parts, to be irradiated.
The preparation of liquor sample: take appropriate rhodamine B, concentration is become to be the solution of 0.4mg/mL with dissolve with ethanol, the amount of solution of preparation is no less than 50mL, get 40mL, be diluted to 100mL with ultrapure water, be mixed with the rhodamine B solution of 0.16mg/mL, be sub-packed in 2 20mL transparent plastic bottles, 10mL in each bottle, sample solution is scarlet, to be irradiated.
Step 2, irradiation-induced degradation:
Utilize X-ray biological irradiation device to obtain a copy of it solid sample to step 1 and liquor sample carries out irradiation, accumulative irradiation dose is 2.7kGy, and solid sample outward appearance is without noticeable change, and liquor sample becomes light pink colour.
The gamma-radiation that another part of solid sample and liquor sample adopt cobalt-60 to produce is carried out irradiation, and accumulative irradiation dose is 2.7kGy, and after irradiation, solid sample outward appearance is without considerable change, and liquor sample lighter, is become in pale pink from scarlet.
Embodiment 3
Step 1, sample prepares:
The preparation of solid sample: take 90mg rhodamine B (purity >99%) and be loaded in 1.5mL transparent plastics centrifuge tube, parallelly takes 2 parts, to be irradiated.
The preparation of liquor sample: take appropriate rhodamine B, concentration is become to be the solution of 0.45mg/mL with dissolve with ethanol, the amount of solution of preparation is no less than 50mL, get 40mL, be diluted to 100mL with ultrapure water, be mixed with the rhodamine B solution of 0.18mg/mL, be sub-packed in 2 20mL transparent plastic bottles, 13mL in each bottle, sample solution is scarlet, to be irradiated.
Step 2, irradiation-induced degradation:
A copy of it solid sample utilizing X-ray biological irradiation device to obtain step 1 and liquor sample carry out irradiation, and accumulative irradiation dose is 3kGy, and solid sample outward appearance is without noticeable change, and liquor sample becomes light pink colour.
The gamma-radiation that another part of solid sample and liquor sample adopt cobalt-60 to produce is carried out irradiation, and accumulative irradiation dose is 3kGy, and after irradiation, solid sample outward appearance is without considerable change, and liquor sample lighter, is become in pale pink from scarlet.
Embodiment 4
Step 1, sample prepares:
The preparation of solid sample: take 100mg rhodamine B (purity >99%) and be loaded in 1.5mL transparent plastics centrifuge tube, parallelly takes 2 parts, to be irradiated.
The preparation of liquor sample: take appropriate rhodamine B, concentration is become to be the solution of 0.5mg/mL with dissolve with ethanol, the amount of solution of preparation is no less than 50mL, get 40mL, be diluted to 100mL with ultrapure water, be mixed with the rhodamine B solution of 0.2mg/mL, be sub-packed in 2 20mL transparent plastic bottles, 15mL in each bottle, sample solution is scarlet, to be irradiated.
Step 2, irradiation-induced degradation:
Utilize X-ray biological irradiation device to obtain a copy of it solid sample to step 1 and liquor sample carries out irradiation, accumulative irradiation dose is 3.3kGy, and solid sample outward appearance is without noticeable change, and liquor sample becomes light pink colour.
The gamma-radiation that another part of solid sample and liquor sample adopt cobalt-60 to produce is carried out irradiation, and accumulative irradiation dose is 3.3kGy, and after irradiation, solid sample outward appearance is without considerable change, and liquor sample lighter, is become in pale pink from scarlet.
The degradation effect of rhodamine B after irradiation in embodiment is analyzed:
The degraded situation of high performance liquid chromatography to the rhodamine B solid after irradiation and solution is utilized to carry out detection analysis.
Solid sample is analyzed: take the rhodamine B solid after pre-irradiation and irradiation respectively and be about 5mg, dissolve constant volume with acetonitrile, then use the solution of acetonitrile stepwise dilution to 1 μ g/mL, sample detection.
Solution example is analyzed: get the rhodamine B solution after pre-irradiation and irradiation respectively, with dilution in acetonitrile to 1 μ g/mL, and sample detection.
When irradiation dose is 2.7 ~ 3.3kGy, after pre-irradiation, the liquid chromatography of rhodamine B solid sample and liquid sample respectively as depicted in figs. 1 and 2.
Interpretation of result: (1) adopts X-ray biological irradiation device to carry out irradiation, when irradiation dose is respectively 0.9kGy, 1.0kGy, 1.1kGy, the degradation rate of rhodamine B solid sample is 4.5%, 3.9%, 4.2%, and the degradation rate of rhodamine B solution is 38.8%, 42.1%, 39.3%.When irradiation dose is respectively 2.7kGy, 3.0kGy, 3.3kGy, the degradation rate of rhodamine B solid sample is 13.9%, 13.5%, 12.3%, and the degradation rate of rhodamine B solution is 98.9%, 98.1%, 99.3%.(2) adopt gamma-radiation irradiation, when irradiation dose is respectively as 2.7kGy, 3.0kGy, 3.3kGy, the degradation rate of rhodamine B solid sample is 12.5%, 13.7%, 14.2%, and the degradation rate of rhodamine B solution is 99.2%, 98.5%, 99.9%.
Irradiation-induced degradation product analysis:
Ultra Performance Liquid Chromatography-series connection high resolution mass spectrum is utilized to carry out detecting analyzing to the radiolysis products after the rhodamine B (as shown in Figure 3) of pre-irradiation and rhodamine B irradiation respectively.Through full scan examination, find radiolysis products 2 in the rhodamine B solution after irradiation, as shown in Figure 4.The molecular ion peak mass-to-charge ratio of the Ultra Performance Liquid Chromatography-QExactive high resolution mass spec mensuration of rhodamine B and radiolysis products thereof is in table 2, tentatively can determine the accurate molecular weight of radiolysis products, the molecular weight of radiolysis products 1 is 165.12, and the molecular weight of radiolysis products 2 is 240.13.Then high resolution mass spectrum is utilized to carry out second order ms scanning to the former medicine of rhodamine B, rhodamine B radiolysis products 1, rhodamine B radiolysis products 2, ms fragment is shown in Fig. 5, Fig. 6, Fig. 7 respectively, tentatively can infer the chemical structural formula of radiolysis products, the molecular formula of radiolysis products 1 is C
10h
15nO, the molecular formula of radiolysis products 2 is C
19h
19nO
3.
The UPLC-QExactiveMS measurement result of table 2 rhodamine B and radiolysis products thereof
Claims (7)
1. a degradation method for rhodamine B, is characterized in that, specifically implements according to the following steps: prepare rhodamine B solid or liquor sample; X-ray or gamma-radiation is utilized to carry out irradiation-induced degradation to rhodamine B sample.
2. the degradation method of a kind of rhodamine B according to claim 1, is characterized in that, the preparation of described rhodamine B liquor sample, is specially: dissolved in ethanol by rhodamine B solid, then with ultrapure water dilution, obtains rhodamine B liquor sample.
3. the degradation method of a kind of rhodamine B according to claim 2, is characterized in that, the concentration of described rhodamine B-ethanolic soln is 0.4 ~ 0.5mg/mL, and the concentration of the rhodamine B liquor sample after dilution is 0.16 ~ 0.2mg/mL.
4. the degradation method of a kind of rhodamine B according to claim 1, is characterized in that, in described rhodamine B solid sample X-x ray irradiation x degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
5. the degradation method of a kind of rhodamine B according to claim 1, is characterized in that, in described rhodamine B liquor sample X-x ray irradiation x degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
6. the degradation method of a kind of rhodamine B according to claim 1, is characterized in that, in described rhodamine B solid sample gamma-radiation irradiation-induced degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
7. the degradation method of a kind of rhodamine B according to claim 1, is characterized in that, in described rhodamine B liquor sample gamma-radiation irradiation-induced degradation process, accumulative irradiation dose is 2.7 ~ 3.3kGy.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107716537A (en) * | 2017-09-08 | 2018-02-23 | 水利部交通运输部国家能源局南京水利科学研究院 | A kind of advanced oxidation reaction unit for purifying petroleum-contaminated soil |
| CN114230433A (en) * | 2021-12-27 | 2022-03-25 | 郑州海阔光电材料有限公司 | Synthetic method of 2-bromo-4 '-chloro-1, 1' -biphenyl |
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| JP2004337785A (en) * | 2003-05-16 | 2004-12-02 | Fuji Photo Film Co Ltd | Method for treating photographic wastewater |
| CN101717170A (en) * | 2009-11-03 | 2010-06-02 | 上海大学 | Method for treating printing and dyeing wastewater by combing electron beam irradiation and biochemistry |
| CN103435206A (en) * | 2013-08-15 | 2013-12-11 | 清华大学 | Organic wastewater ozonation and ionizing radiation synergetic treatment method and treatment system |
| CN105126743A (en) * | 2015-08-20 | 2015-12-09 | 南京航空航天大学 | Preparation and recovery methods for magnetic clay adsorption material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004337785A (en) * | 2003-05-16 | 2004-12-02 | Fuji Photo Film Co Ltd | Method for treating photographic wastewater |
| CN101717170A (en) * | 2009-11-03 | 2010-06-02 | 上海大学 | Method for treating printing and dyeing wastewater by combing electron beam irradiation and biochemistry |
| CN103435206A (en) * | 2013-08-15 | 2013-12-11 | 清华大学 | Organic wastewater ozonation and ionizing radiation synergetic treatment method and treatment system |
| CN105126743A (en) * | 2015-08-20 | 2015-12-09 | 南京航空航天大学 | Preparation and recovery methods for magnetic clay adsorption material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107716537A (en) * | 2017-09-08 | 2018-02-23 | 水利部交通运输部国家能源局南京水利科学研究院 | A kind of advanced oxidation reaction unit for purifying petroleum-contaminated soil |
| CN114230433A (en) * | 2021-12-27 | 2022-03-25 | 郑州海阔光电材料有限公司 | Synthetic method of 2-bromo-4 '-chloro-1, 1' -biphenyl |
| CN114230433B (en) * | 2021-12-27 | 2023-10-20 | 郑州海阔光电材料有限公司 | Synthesis method of 2-bromo-4 '-chloro-1, 1' -biphenyl |
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Application publication date: 20160302 |