CN104556292A - Method for photochemical degradation of sulfonamide in water by using freshwater algae - Google Patents
Method for photochemical degradation of sulfonamide in water by using freshwater algae Download PDFInfo
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- CN104556292A CN104556292A CN201310524347.1A CN201310524347A CN104556292A CN 104556292 A CN104556292 A CN 104556292A CN 201310524347 A CN201310524347 A CN 201310524347A CN 104556292 A CN104556292 A CN 104556292A
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- algae
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
- C02F3/322—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
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- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention relates to a method for photochemical degradation of sulfonamide in water by using freshwater algae. A sulfonamide in water is degraded by utilizing active oxygen produced by the freshwater algae. The specific implementation method is as follows: wastewater to be treated is introduced into a reactor in a circulating way, and the active oxygen matter produced by light radiation on the freshwater algae is used for degrading the sulfonamide when the ventilatory capacity is 0.5L/min and the pH value is 6 at certain alga concentration and temperature. The reaction time is prolonged, the concentration of the sulfonamide is reduced, and the effluent which meets the requirements can be finally achieved.
Description
Technical field
The present invention relates to the method for sulfonamide in a kind of algae photochemical degradation water, provide a kind of environmental friendliness, efficient, cheap photochemistry ecological method to repair the technology of polluted-water.
Background technology
Sulfanilamide (SN) is the medicine that a class is widely used in treatment infection.After humans and animals takes sulfonamide, the part of non-metabolism enters in water surrounding with movement.In addition, along with the development of intensive culture industry, sulfonamide gets more and more in culture fishery as fodder additives, and feed directly applies at the water surface by raiser, and the feed a part containing medicine is not eaten by animal and directly enters in water.Therefore all detect certain density sulfonamide in different areas, different water body, cause certain harm to the ecotope of receiving water body.
Photochemical method has efficient, simple, nontoxic, cheap advantage, is widely used in the organism removed organism in water difficult degradation or have pharmaceutical activity.At present, photochemical method as catalysis medium, but easily causes metal catalytic medium to enter in processed water with different valence state mainly with metal, and cause potential hazard to the aquatic animals and plants of receiving water body, therefore photochemistry ecological method degradation water Chinese traditional medicine is developing direction.But in photochemistry ecological method degradation water, organic research is also few, and rarely has report for having pharmaceutical activity antibiotic substance in water especially.
Algae is a class eukaryotic microorganisms, aquatic and can carry out photosynthesis.Algae is in light action, and cell inner chlorophyll can produce hydrated electron and hole, and the two produces hydrogen peroxide and molecular oxygen after serial reaction, and hydrogen peroxide can produce hydroxy radical qiao.Therefore; light-initiated fresh water algae produce hydrogen peroxide can be degradable organic pollutant, restoration of the ecosystem polluted water body opens new way; Given this fresh water algae can be utilized as catalysis medium; sulfonamide in photochemical degradation water surrounding; the water body that restoration of the ecosystem is polluted, has very profound significance to the protection of water surrounding.
Summary of the invention
The invention provides a kind of photochemical method that can remove sulfonamide in degradation water, to realize antibiotic medicine in environmental friendliness, ecology, efficient, cheap degradation water, be applicable to the waste water of process containing the cultivation of sulfonamide, life and production.
The method of sulfonamide in a kind of algae photochemical degradation water of the present invention:
The device of a step 1 photochemical degradation sulfonamide method, comprises reactor, magnetic stirring apparatus, air pump, Controlling System, mercury lamp, storage tank, as shown in Figure 1.Reactor is provided with water inlet pipe and rising pipe, mercury lamp is placed in quartzy chuck in reactor.
Step 2 regulates sulfonamide waste water ph, adds a certain amount of algae, is placed in storage tank.
Step 3 opens constant flow pump, and waste water enters in reactor.Open water recycle pump, keeps water flow in quartzy chuck, constant
Temperature (25 DEG C) during reaction.Open air pump, regulate spinner-type flowmeter, be constant at 0.5L/min.
Step 4 opening control system, arranges the reaction times, opens magnetic stirring apparatus, stirs waste water, opens mercury lamp after stablizing 1-2min, starts to carry out the reaction of algae photochemical degradation sulfonamide, timing sampling, and the concentration measuring sulfonamide in water.
Step 5 is when in water, sulfonamide is lower than set concentration, stopped reaction.
Compared with prior art, advantage of the present invention:
1. algae is biology more common in a kind of river, lake, cheap and easy to get, and does not produce secondary pollution, is a kind of eco-friendly photochemical Intermediate.
In 2.60min, concentration of algae is 2 × 10
9individual/L time, sulfonamide degraded can reach more than 50%.
3. because of not metal ion or metallic compound in the water after process, without the need to secondary treatment, therefore on the water microorganisms of receiving water body without impact.
4. algae cheap and easy to get, can save working cost greatly.
5. this technique can manual operation, also can realize semi-automation and full-automatic operation.
Accompanying drawing explanation
Fig. 1 reaction unit figure
Fig. 2 controlled trial figure
Fig. 3 concentration of algae and degradation rate relation
Fig. 4 pH and degradation rate relation
Fig. 5 temperature and degradation rate relation
Fig. 6 concentration of substrate and degradation rate relation
Embodiment
Embodiment 1
The Sulphadiazine Sodium waste water of dress 3L in storage tank (long 20cm, wide 20cm, high 15cm), pH value is adjusted to about 6, adds the algae (2 × 10 of some amount
9individual frustule/L), open constant flow pump, make pending waste water enter reactor, flow velocity is 0.3L/min.
Step 1 ON cycle water pump, keep the circulation of quartz reactor jacket water (J.W.), recirculated water flow velocity is 1L/min, and the aqueous solution in reactor maintains room temperature (about 25 DEG C).
Step 2 opens air pump, regulates the spinner-type flowmeter be connected with reactor, is constant at 0.5L/min.
Step 3 opening control system, arranges the reaction times, and interval 10min alarm sampling and testing, then open magnetic stirring apparatus, stir pending waste water, rotating speed is set to 100 turns/min.
After step 4 system stability 1-2min, open the mercury lamp (power is 25W) in reactor, interval 10min samples, and makes
The concentration of Sulphadiazine Sodium in water is measured with HPLC.
After step 5 reaches set concentration (in 60min, degradation rate reaches more than 50%), mercury lamp in off-response device, stops stirring, ventilating, then cuts out water circulating pump switch, and cut out constant flow pump switch.
Embodiment 2
The sulfametoxydiazine waste water of dress 3L in storage tank (long 20cm, wide 20cm, high 15cm), pH value is adjusted to about 6, adds the algae (2 × 10 of some amount
9individual frustule/L), open constant flow pump, make pending waste water enter reactor, flow velocity is 0.3L/min.
Step 1 ON cycle water pump, keep the circulation of quartz reactor jacket water (J.W.), recirculated water flow velocity is 1L/min, and the aqueous solution in reactor maintains room temperature (about 25 DEG C).
Step 2 opens air pump, regulates the spinner-type flowmeter be connected with reactor, is constant at 0.5L/min.
Step 3 opening control system, arranges the reaction times, and interval 10min alarm sampling and testing, then open magnetic stirring apparatus, stir pending waste water, rotating speed is set to 100 turns/min.
After step 4 system stability 1-2min, open the mercury lamp (power is 25W) in reactor, interval 10min samples, and uses HPLC to measure the concentration of sulfametoxydiazine in water.
After step 5 reaches set concentration (in 60min, degradation rate reaches more than 50%), mercury lamp in off-response device, stops stirring, ventilating, then cuts out water circulating pump switch, and cut out constant flow pump switch.
With reference to the accompanying drawings, description is in more detail made to the present invention:
1. the method for sulfonamide in algae photochemical degradation water
The determination of 1.1 algae photochemical degradation effects
Fig. 2 is the contrast degradation experiment of 20mg/L Sulphadiazine Sodium and sulfametoxydiazine.As can be seen from Figure 2, concentration of algae is 2 × 10
8individual/L and unglazed according to time, the Sulphadiazine Sodium degradation rate after 60min is the sulfametoxydiazine degradation rate after 6.36%, 60min is 5.34%; Concentration of algae is 2 × 10
8individual/L and when having illumination, the Sulphadiazine Sodium degradation rate after 60min is the sulfametoxydiazine degradation rate after 42.78%, 60min is 38.86%.So, rayed algae sulfa drugs capable of being fast degraded.
The determination of 1.2 concentration of algae
With four groups of different concentration of algae, analyze concentration of algae to the impact of reaction system.As seen from Figure 3, concentration of algae is 2.0 × 10
6-2.0 × 10
9time between individual/L, Sulphadiazine Sodium and sulfametoxydiazine concentration are 20mg/L, the photodegradation rate of Sulphadiazine Sodium and sulfametoxydiazine all increases along with the increase of concentration of algae, this is because concentration of algae is higher, the reactive oxygen species produced is also more, and the photodegradation rate of Sulphadiazine Sodium and sulfametoxydiazine then increases.But, the penetrance of light can be had influence on when concentration of algae is too high, be unfavorable for that illumination is mapped on frustule, therefore concentration of algae is not suitable for too high, pool 2 × 10 should be selected
9comparatively suitable.
The determination of 1.3pH
Analyze pH to Sulphadiazine Sodium, the photodegradative impact of sulfametoxydiazine, concentration of algae is 2 × 10
9individual/L, Sulphadiazine Sodium and sulfametoxydiazine concentration are 20mg/L, and sample pH value is respectively 4,5,6.After 60min UV illumination, its degraded situation of the Sulphadiazine Sodium in sample, sulfametoxydiazine as shown in Figure 4.Experimental result shows that Sulphadiazine Sodium, the sulfametoxydiazine degradation rate in algae solution is higher when pH value is 6, and wherein the photodegradation rate of Sulphadiazine Sodium is 60.31%, and the photodegradation rate of sulfametoxydiazine is 55.52%.Under the condition of acidity, the activity of algae is lower, and the survive pH value of best water surrounding of algae is 6 to 8, and when pH is 6, the degradation rate of Sulphadiazine Sodium and sulfametoxydiazine is higher may be the formation being beneficial to reactive oxygen species in weakly acidic condition.
The determination of 1.4 temperature
As shown in Figure 5, be 2 × 10 at concentration of algae
9individual/L, Sulphadiazine Sodium and sulfametoxydiazine concentration are 20mg/L, and when sample pH value is 6, temperature is 20 DEG C-30 DEG C these temperature ranges, and degradation effect is relatively good.During initial analysis 25 DEG C, algae growth is the most active, and intracellular reactive material is maximum, and when the temperature decreases, Growth of Cells is suppressed, active reduction; When in like manner temperature raises, Growth of Cells is suppressed, active reduction, but when temperature is raised to a certain degree, show as between 30 DEG C-35 DEG C in this article, part frustule may be damaged, active substance in cell flows in solution, affects the degradation rate of Sulphadiazine Sodium and sulfametoxydiazine.
1.5 concentration of substrate are determined
The relation of concentration of substrate and its degradation rate is shown in Fig. 6, and the concentration range of Sulphadiazine Sodium and sulfametoxydiazine is 10-30mg/L.As shown in Figure 6, when starting point concentration is 10mg/L, after illumination 20min, the degradation rate of Sulphadiazine Sodium just reaches 90.1%; And when starting point concentration increases to 30mg/L, after illumination 60min, photodegradation rate also only has 52.9%.The degradation rate of the lower then Sulphadiazine Sodium of starting point concentration is higher, leads to the same conclusion for sulfametoxydiazine.Therefore, lower concentration sulfamido waste water should be selected to carry out DeR.
1.6 analysis and summary
To sum up experimental result, controls suitable pH, concentration of algae, temperature and concentration of substrate, can improve the degradation rate of sulfanilamide (SN), Reaction time shorten, reduces processing cost.
The determination of 2 device parameters
The pH of algae photochemical degradation sulfanilamide (SN) should control 6, and concentration of algae controls 2 × 10
9individual/L, temperature controls at 25 DEG C, concentration of substrate 20mg/L and following.
Claims (5)
1. the method for sulfonamide in an algae photochemical degradation water, it is characterized in that by containing algae sulfonamide waste water introduce air-blowing stir reactor in and apply ultraviolet lighting, sulfonamide by algae produce activating oxide degrade, sulfonamide is decomposed into small organic molecule and inorganics gradually.
2. according to the method for algae photochemical degradation sulfonamide in claim 1, it is characterized in that in reactor water, algae concentration must maintain certain concentration of algae, 100 turns/min stirs water body and passes into certain flow rate air bubbling, and algae fully can contact with the oxygen in water.
3. according to the method for algae photochemical degradation sulfonamide in claim 1, it is characterized in that the ultraviolet lighting that must have more than 25W, make light homogeneous radiation on frustule, ultraviolet excitation algae and secretory product produce activating oxide degraded sulfonamide.
4., according to the method for algae photochemical degradation sulfonamide in claim 1, it is characterized in that sulfanilamide (SN) contained by water body must under 20mg/L condition, to ensure the degradation rate of sulfonamide.
5. according to the method for algae photochemical degradation sulfonamide in claim 1, it is characterized in that the temperature of water body in reactor must control at about 25 DEG C, water body pH controls 6, to ensure that algae survives, produces activating oxide.
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| CN201310524347.1A CN104556292A (en) | 2013-10-28 | 2013-10-28 | Method for photochemical degradation of sulfonamide in water by using freshwater algae |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692861A (en) * | 2016-03-21 | 2016-06-22 | 南京大学 | Advanced oxidation method for removing artificial sweetener in sewage |
| CN107144649A (en) * | 2017-04-26 | 2017-09-08 | 西安理工大学 | Biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine |
| CN110330104A (en) * | 2019-06-21 | 2019-10-15 | 临沂大学 | A method of with p-aminobenzoic acid in microorganism removal water body |
-
2013
- 2013-10-28 CN CN201310524347.1A patent/CN104556292A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692861A (en) * | 2016-03-21 | 2016-06-22 | 南京大学 | Advanced oxidation method for removing artificial sweetener in sewage |
| CN105692861B (en) * | 2016-03-21 | 2018-07-27 | 南京大学 | The advanced oxidization method of artificial sweetener in a kind of removal sewage |
| CN107144649A (en) * | 2017-04-26 | 2017-09-08 | 西安理工大学 | Biodegrading process based on ultrasonic or ultraviolet enhanced sulfamethyldiazine |
| CN110330104A (en) * | 2019-06-21 | 2019-10-15 | 临沂大学 | A method of with p-aminobenzoic acid in microorganism removal water body |
| CN110330104B (en) * | 2019-06-21 | 2022-04-29 | 临沂大学 | Method for removing p-aminobenzoic acid in water body by using microorganisms |
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Application publication date: 20150429 |