CN105776748A - Method for degrading bisphenol A in wastewater with chlorella combined with metal ions - Google Patents

Method for degrading bisphenol A in wastewater with chlorella combined with metal ions Download PDF

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Publication number
CN105776748A
CN105776748A CN201610217098.5A CN201610217098A CN105776748A CN 105776748 A CN105776748 A CN 105776748A CN 201610217098 A CN201610217098 A CN 201610217098A CN 105776748 A CN105776748 A CN 105776748A
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bisphenol
waste water
chlorella
wastewater
illumination
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不公告发明人
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Guangzhou Juzhu Patent Research And Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • C02F1/32Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/32Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
    • C02F3/322Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae use of algae

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides a method for degrading bisphenol A in wastewater with chlorella combined with metal ions. The method includes the steps that a chlorella solution is prepared and added into wastewater with the initial concentration of bisphenol A being 0.5-3 mg/L by the volume fraction (mL/L) of 1-6, the pH value is adjusted to be 3.5-6.5, 0.5-1 mL of 5 mol/L aluminum chloride or ferric chloride solution is added, the reaction solution is fully mixed through stirring for 2 min, and treated wastewater is obtained after illumination for 30-120 min. The method is obvious in effect of degrading bisphenol A in the wastewater.

Description

A kind of utilize the method for bisphenol-A in chlorella bind metal ion degrading waste water
Technical field
The invention belongs to sewage treatment area, be specifically related to and utilize the method for bisphenol-A in chlorella bind metal ion degrading waste water.
Background technology
Bisphenol-A, formal name used at school 2,2-bis-(4-hydroxy phenyl) propane, is called for short BPA.It is synthesized under acid medium by phenol and acetone, not naturally occurring.It is mainly for the production of multiple macromolecular materials such as Merlon, epoxy resin, polysulfone resin, polyphenylene oxide resin, unsaturated polyester resins.It can also be used for producing the fine chemical products such as plasticizer, fire retardant, antioxidant, heat stabilizer, rubber antioxidant, pesticide, coating.It is ubiquitous industrial chemicals in a kind of daily life, also pollutes environment while facilitating the mankind.Bisphenol-A is similar to estrin structure, has estrogen activity, belongs to incretion interferent.A lot of countries have limited production and the use of bisphenol-A, and it has become as one of environmental contaminants, is all detected in water, soil etc..Bisphenol-A in water body is enriched with by aquatic animals and plants, again through food chain by bisphenol-A indirect transfer to other biological and the mankind, thus biological and the reproductive system of the mankind, immune system and nervous system are had undesirable effect, and then a series of disease occurs.
Tradition is removed bisphenol-A in waste water and is mostly adopted Physical and chemical method.Physical absorption completes by Van der Waals force between molecule, easy and simple to handle, but bisphenol-A is not really removed by this method from environment, under certain condition, it may occur that desorbing, causes secondary pollution.Chemical removal method degradation efficiency is high, and bisphenol-A has low concentration effect, and when interferent concentration during bisphenol A concentration is lower than waste water, it is relatively costly that removal bisphenol-A needs to its Standard Safety Margin, complicated operation.It would therefore be highly desirable to find a kind of method that safe and simple, non-secondary pollution removes bisphenol-A.
Algae is the autophyte with photosynthetic pigments the most original on the earth, it is possible to by photosynthesis inorganic matter synthesis of organic substance for self growth needs.Algae strong adaptability, can survive in various environment, and primary growth is in water, and has a very wide distribution.Chlorella Chlorophyceae, chlorella section, include chlorophyll, single-cell algae, Chang Dansheng, also have many cells to assemble.Chlorella is distributed widely in nature, with freshwater most species, it is easy to cultivates, can not only utilize auto-trophy, moreover it is possible to utilize organic carbon source to carry out growing and breeding under different oxygen condition, and growth and breeding speed is fast.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art with not enough, it is provided that a kind of to utilize the method for bisphenol-A in chlorella bind metal ion degrading waste water.
The present invention is realized by following technical scheme:
Chlorella culture fluid composition: NH4NO31.0~1.5g, K2HPO40.03~0.04g, MgSO4.7H2O0.06~0.07g, Na2CO30.02~0.025g, ferric citrate amine 0.004~0.005g, EDTA-Na20.001~0.002g, citric acid 0.005~0.007g, CaCl20.03~0.035g, 1~2mL trace element mixed liquor, adds distilled water to 1L, regulates pH=7.0~7.5, in 1.103MPa, and sterilizing 20min, wherein CaCl under 121 DEG C of conditions2Individually carry out sterilizing.After culture fluid is cooled to room temperature, aseptically, add sterilized calcium chloride, shake up, inoculation.Being positioned over by postvaccinal culture fluid in 28 DEG C of constant temperature illumination boxs and cultivate, intensity of illumination is 4000~6500lux, every switching in 7~10 days once.Every day, timing was rocked 2~3 times, transfers and cultivates to obtain bead algae solution after three times.
Bead algae solution by volume mark (mL/L) 1~6 is added in the waste water that initial bisphenol A concentration is 0.5~2.5mg/L, regulate pH=3.5~6.5, add 5mol/L aluminum chloride or the ferric chloride solution of 0.5~1mL, stir 2 minutes, make reactant liquor be sufficiently mixed, open uviol lamp or electric filament lamp carries out illumination.After illumination 30min~120min, obtain the waste water after process.
Preferably, described pH regulator ranges for 3.5~5.
Preferably, described light application time is 60~90min.
Preferably, described bisphenol-A initial concentration is 0.5~2.0mg/L.
Preferably, described bead algae solution addition is 2~5 (mL/L).
Bisphenol-A detection method in the present invention adopts high performance liquid chromatograph to measure, and design parameter condition: take a certain amount of reactant liquor carries out chromatography after 0.45 μm of membrane filtration, and chromatographic column is C18(4.6 × 150mm, 5 μm), UV detector, wavelength 278nm, column temperature 35 DEG C, mobile phase acetonitrile: water=60:40 (v/v), flow velocity is 1mL/min, sampling volume 20 μ L.
Accompanying drawing explanation
Fig. 1 is the impact that bisphenol-A is degraded by chlorella addition.
Fig. 2 is the impact that bisphenol-A is degraded by pH value.
Fig. 3 is the impact that bisphenol-A is degraded by initial bisphenol A concentration.
Fig. 4 is the impact that bisphenol-A is degraded by metal ion.
Detailed description of the invention
Understand to make the technological means of the present invention be easier to, be further described below below in conjunction with specific embodiment, but embodiments of the present invention are not limited to this.
Embodiment of the present invention bead algae solution adopts following steps to cultivate gained:
Triangular flask adds NH4NO31.5g, K2HPO40.04g, MgSO4.7H2O0.06g, Na2CO30.02g, EDTA-Na20.001g, ferric citrate amine 0.004g, citric acid 0.006g, 1mL trace element mixed liquor, add distilled water to 1L, regulate pH=7.0, in 1.103MPa, sterilizing 20min, CaCl under 121 DEG C of conditions20.03g individually carries out sterilizing.After culture fluid is cooled to room temperature in triangular flask, aseptically, add sterilized calcium chloride, shake up, obtain chlorella culture fluid.Being positioned in 28 DEG C of constant temperature illumination boxs after chlorella is inoculated into the culture fluid prepared and cultivate, intensity of illumination is 5000lux, every switching in 7 days once.Every day, timing was rocked 2~3 times, transfers and cultivates to obtain bead algae solution after three times.
The trace element mixed liquor that the present embodiment uses is containing H3BO32.86mg, MnCl2.4H2O1.86mg, ZnSO4.7H2O0.22mg, Na2MoO4.2H2O0.39mg, CuSO4.5H2O0.08mg, Co (NO3)2.6H2O0.05mg。
The present invention adopts high performance liquid chromatography detection content of bisphenol A, takes a certain amount of reactant liquor, carries out chromatography after 0.45 μm of membrane filtration, and chromatographic column is C18(4.6 × 150mm, 5 μm), UV detector, wavelength 278nm, column temperature 35 DEG C, mobile phase is acetonitrile: water=60:40 (v/v), and flow velocity is 1mL/min, sampling volume 20 μ L.
Embodiment 1: the impact that bisphenol-A is degraded by bead algae solution addition.
Process object is bisphenol-A initial concentration is the waste water of 2.0mg/L, bead algae solution difference by volume mark (mL/L) is in 1,2,3,4,5,6 addition waste water, regulate pH to 5, add the liquor alumini chloridi of the 5mol/L of 0.5mL, stir 2 minutes, open uviol lamp to be irradiated, a sample is taken every 15min, then measure the bisphenol A concentration in sample with high performance liquid chromatograph and calculate degradation rate, bisphenol-A degradation rate (%)=(after initial concentration-reaction concentration in water)/initial concentration × 100%, result is shown in such as Fig. 1.
As seen from the figure, in algae solution addition within the scope of 1~5mL/L, along with algae solution addition increases, bisphenol-A degradation rate increases, and under 4mL/L addition, illumination 120min, bisphenol-A degradation rate is 91.2%.When algae solution addition > 5mL/L time, bisphenol-A degradation rate occur decline.
The impact that bisphenol-A is degraded by embodiment 2:pH value.
Process object is bisphenol-A initial concentration is the waste water of 1.5mg/L, by volume mark (mL/L) is 5 addition bead algae solutions, regulate pH to 3,3.5,4,5,6,6.5,7 respectively, add the liquor alumini chloridi of the 5mol/L of 0.5mL, stir 2 minutes, open uviol lamp and be irradiated, take a sample every 15min, then measuring the bisphenol A concentration in sample with high performance liquid chromatograph and calculate degradation rate, result is shown in such as Fig. 2.
As seen from the figure, pH is very big on bisphenol-A degraded impact, and as 3 pH 5, along with pH raises, bisphenol-A degradation rate increases, and when pH=5, illumination 105min, bisphenol-A degradation rate is up to 90.3%.As pH > 6 time, bisphenol-A degradation rate decline, under pH=7, illumination 120min bisphenol-A degradation rate is 75%.
Embodiment 3: the impact that bisphenol-A is degraded by bisphenol-A initial concentration.
Process the waste water that object is bisphenol-A initial concentration respectively 0.5mg/L, 1.0mg/L, 1.5mg/L, 2.0mg/L, 2.5mg/L, 3.0mg/L, 3.5mg/L, by volume mark (mL/L) is 4 addition bead algae solutions, regulate pH to 4.5, add the ferric chloride solution of the 5mol/L of 1mL, stir 2 minutes, open uviol lamp and be irradiated, take a sample every 15min, then measuring the bisphenol A concentration in sample with high performance liquid chromatograph and calculate degradation rate, result is shown in such as Fig. 3.
As seen from the figure, bisphenol-A initial concentration is more low, and bisphenol-A degradation rate is more big.When light application time is 90min, when bisphenol-A initial concentration is 0.5mg/L, 1.0mg/L, 1.5mg/L, 2.0mg/L, bisphenol-A degradation rate respectively 90%, 89%, 86%, 82%, and under same light application time, bisphenol-A initial concentration is the reactant liquor of 3.0mg/L, and bisphenol-A degradation rate is 73%.
Embodiment 4: the impact that bisphenol-A is degraded by metal ion
Process object is bisphenol-A initial concentration is the waste water of 1.0mg/L, by volume mark (mL/L) is 5 addition bead algae solutions, regulate pH to 4.5, add the ferric chloride solution of the 5mol/L of 1mL, stir 2 minutes, open uviol lamp to be irradiated, take a sample every 15min, then measure the bisphenol A concentration in sample with high performance liquid chromatograph and calculate degradation rate.Ferric chloride solution, repeat the above steps is replaced with liquor alumini chloridi.Replace iron chloride or liquor alumini chloridi again with deionized water, repeat the above steps, as the matched group of the present embodiment.Result is shown in such as Fig. 4.
There is figure it can be seen that interpolation bead algae solution adds aluminum chloride or ferric chloride solution bisphenol-A degradation rate is higher than bisphenol-A degradation rate when individually adding bead algae solution simultaneously.
The preferred algae solution addition of this method is 3~5 (mL/L), pH is 3.5~6.5, bisphenol-A initial concentration is 0.5~2.0mg/L, light application time is 60~90min, and bisphenol-A degradation effect is best.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are also not restricted to the described embodiments; other any does not run counter to change that the principle of the invention makees, modification, combination, replacement, is the substitute mode of equivalence, is included within protection scope of the present invention.

Claims (6)

1. one kind utilizes the method for bisphenol-A in chlorella bind metal ion degrading waste water, it is characterised in that chlorella culture fluid composition: NH4NO31.0~1.5g, K2HPO40.03~0.04g, MgSO4.7H2O0.06~0.07g, Na2CO30.02~0.025g, ferric citrate amine 0.004~0.005g, EDTA-Na20.001~0.002g, citric acid 0.005~0.007g, CaCl20.03~0.035g, 1~2mL trace element mixed liquor, adds distilled water to 1L, regulates pH=7.0~7.5, in 1.103MPa, and sterilizing 20min, wherein CaCl under 121 DEG C of conditions2Individually carry out sterilizing.After culture fluid is cooled to room temperature, aseptically, add sterilized calcium chloride, shake up, inoculation.Being positioned over by postvaccinal culture fluid in 28 DEG C of constant temperature illumination boxs and cultivate, intensity of illumination is 4000~6500lux, every switching in 7~10 days once;Every day, timing was rocked 2~3 times, transfers and cultivates to obtain bead algae solution after three times;Bead algae solution by volume mark (mL/L) 1~6 is added in the waste water that initial bisphenol A concentration is 0.5~2.5mg/L, regulate pH=3.5~6.5, add 5mol/L aluminum chloride or the ferric chloride solution of 0.5~1mL, stir 2 minutes, reactant liquor is made to be sufficiently mixed, open uviol lamp or electric filament lamp carries out illumination, after illumination 30min~120min, obtain the waste water after process.
2. bisphenol-A biodegrading process in waste water according to claim 1, it is characterised in that described adjustment containing bisphenol-A wastewater pH adds iron chloride or liquor alumini chloridi after 3.5~6.5.
3. the method for bisphenol-A degraded in waste water according to claim 1 or claim 2, it is characterised in that the described wastewater pH condition and range containing bisphenol-A is preferably 3.5~5.
4. bisphenol-A biodegrading process in waste water according to claim 1, it is characterised in that described light application time is preferably 60~90min.
5. bisphenol-A biodegrading process in waste water according to claim 1, it is characterised in that described bisphenol-A initial concentration is preferably 0.5~2.0mg/L.
6. bisphenol-A biodegrading process in waste water according to claim 1, it is characterised in that described bead algae solution addition is preferably 3~5 (mL/L).
CN201610217098.5A 2016-04-09 2016-04-09 Method for degrading bisphenol A in wastewater with chlorella combined with metal ions Pending CN105776748A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109928586A (en) * 2019-04-28 2019-06-25 重庆工商大学 A kind of method of difficult for biological degradation organic pollutant in removal dyeing waste water

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