CN110357266A - Utilize the method for heavy metal ion in sargassum thunbergii removal polluted-water - Google Patents

Utilize the method for heavy metal ion in sargassum thunbergii removal polluted-water Download PDF

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Publication number
CN110357266A
CN110357266A CN201910634793.5A CN201910634793A CN110357266A CN 110357266 A CN110357266 A CN 110357266A CN 201910634793 A CN201910634793 A CN 201910634793A CN 110357266 A CN110357266 A CN 110357266A
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water
sargassum thunbergii
heavy metal
metal ion
threonine
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CN201910634793.5A
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CN110357266B (en
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马玉心
崔大练
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Zhejiang Ocean University ZJOU
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Zhejiang Ocean University ZJOU
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/10Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G33/00Cultivation of seaweed or algae
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management

Abstract

The present invention is about polluted-water processing, especially with regard to a kind of method using heavy metal ion in sargassum thunbergii removal polluted-water, the carbon dots of soluble doping threonine are synthetically prepared using L-threonine and citric acid first, the carbon dots of above-mentioned soluble doping threonine are added in culture medium and cultivate sargassum thunbergii, then sargassum thunbergii and cyanobacteria, zinc salt and pH adjusting agent are re-dubbed compound sargassum thunbergii preparation, finally compound sargassum thunbergii preparation is put into polluted-water and Aerated stirring is fully absorbed the heavy metal ion in target stains water body.Sargassum thunbergii is cultivated using the carbon dots joint blue light irradiation of the water-soluble doping threonine of the application preparation, the sargassum thunbergii liquid making that there is larger adsorption capacity to heavy metal ion can be obtained, contents of many kinds of heavy metal ion in polluted-water can be effectively removed by being re-dubbed compound formulation, can be widely applied to the treatment process of contaminant water, waste water etc..

Description

Utilize the method for heavy metal ion in sargassum thunbergii removal polluted-water
Technical field
The present invention about polluted-water processing, especially with regard to it is a kind of using sargassum thunbergii removal polluted-water in heavy metal from The method of son.
Background technique
The heavy metal amount of the mankind to environmental emission is increasing, not only seriously polluted water resource, returns mankind's itself Health brings great harm.Currently, the improvement to heavy metal-polluted water generally uses physics, chemistry and biological method, Such as the precipitation method, chelating resin method, macromolecule trapping, natural zeolite absorption method and ion-exchange etc..Above method Purifying rate it is very high, but process flow is mostly very long, and cumbersome, processing cost is expensive.Therefore people, which have been working hard, seeks Seek more environmentally friendly method.Algae is very strong for heavy metal adsorption and accumulation ability, and adsorption capacity is bigger, but it is often adsorbed Rate is slower, and has special selectivity to certain heavy metal elements, it is difficult to accomplish the quick suction of detection device for multi metallic elements It is attached.
Sargassum thunbergii (Sargassumthunbergii) is Phaeophyta (Phaeophyta), Fucales (Fucales), horse One of Wei Zao section (Sargassaceae), Sargassum (Sargassum), China north to Liaodong Peninsula, south to Leizhou half Island is distributed, and is a kind of kelp of intertidal zone.In recent years, the economy and the ecological value of sargassum thunbergii cause the weight of people Depending on one side sargassum thunbergii is the high-quality feed of sea cucumber seedlings, and due to the fast development of holothruian cultures industry, wild resource far can not On the other hand it is the tangleweed of intertidal zone growth that meet demand is due to sargassum thunbergii, and often becomes sociales, biomass Up to 5kg/m2More than, it plays an important role in the environmental ecology reparation of offshore waters.How to realize using sargassum thunbergii to pollution Heavy metal ion in water, which efficiently rapidly absorbs, has more important application prospect and economic value.
The disclosure of background above technology contents is only used for auxiliary and understands inventive concept and technical solution of the invention, not The prior art for necessarily belonging to present patent application shows above content in the applying date of present patent application in no tangible proof In the case where having disclosed, above-mentioned background technique should not be taken to the novelty and creativeness of evaluation the application.
Summary of the invention
The purpose of the present invention is to provide a kind of methods using heavy metal ion in sargassum thunbergii removal polluted-water, utilize Sargassum thunbergii is cultivated in the carbon dots joint blue light irradiation of the water-soluble doping threonine of the application preparation, can be obtained to a huge sum of money Belong to ion have larger adsorption capacity sargassum thunbergii liquid making, be re-dubbed compound formulation can effectively remove it is a variety of heavy in polluted-water Metal ion can be widely applied to the treatment process of contaminant water, waste water etc..
The technical solution that the present invention is taken to achieve the above object are as follows:
[1] a kind of sargassum thunbergii cultural method comprising:
1) algae basis is cultivated: being cultivated the sargassum thunbergii cell inoculation after activation to basis with 0.1 Initial seeding density In base, culture to logarithmic growth phase;
2) it algae optimization culture: takes and is cultivated in step 1) to the rat-tail algae solution of logarithmic growth phase, through centrifugation or filtration washing After obtain algal gel, the nitrogen source being inoculated with into another addition N doping carbon dots is reduced basal medium, and culture is to stabilization under blue light irradiation Phase harvests frustule;
Wherein, the N doping carbon dots are the carbon dots (CDs-Thr) of water-soluble doping threonine;
The intensity of illumination of the blue light irradiation is 1500~2500Lux, and the wavelength of blue light is 440~460nm.
Sargassum thunbergii cultural method step provided by the invention is simple, easily operated, and the speed of growth of sargassum thunbergii is fast, nutrients Matter cumulant is big, while being also used as the raw material of the heavy mental treatment agent of heavy metal ion in removal polluted-water, Sargassum thunbergii liquid making obtained can effectively remove the Cu in polluted-water2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or it is more Kind combination heavy metal ion, can be widely applied to the treatment process of contaminant water, waste water etc..
Basis culture in the present application content and preferred embodiment, in the algae basis incubation step of the step 1) Base composition is as follows: 11.0~15.0g/L of sodium bicarbonate, 0.5~1.0g/L of dipotassium hydrogen phosphate, 3.2~5.2g/L of calcium nitrate, chlorination 3.2~4.0g/L of sodium, 0.12~0.2g/L of magnesium sulfate, 0.01~0.20g/L of ferrous sulfate, 1.25~1.5mg/L of boric acid, sulfuric acid 2.5~5.0mg/L of zinc, 3.0~10.0mg/L of copper sulphate, 2.0~3.0mg/L of cobalt nitrate, remaining is water, pH value 7.0~7.5.
Cultivation temperature in the present application content and preferred embodiment, in the algae basis incubation step of the step 1) It is 25~32 DEG C, 12L/12D is with 3000~4000Lux of intensity of illumination irradiation.
In the present application content and preferred embodiment, the nitrogen source of the addition N doping carbon dots of the step 1) is reduced basis Culture medium is the carbon dots (CDs-Thr) that the water-soluble doping threonine of 55~100mg/L is added in basal medium, and by nitre The content of sour calcium is adjusted to 1.2~1.5g/L.
In the present application content and preferred embodiment, in the step 2), nitrogen of the algal gel through another addition N doping carbon dots It is 0.25~0.35 that source decrement basal medium, which is directly diluted to Initial seeding density,.
In the present application content and preferred embodiment, the cultivation temperature of the algae optimization culture of the step 2) is 30~ 32 DEG C, pH is 7.0~8.0.
In the present application content and preferred embodiment, the carbon dots (CDs- of the water-soluble doping threonine of the step 2) Thr) the preparation method comprises the following steps: weigh 0.20~0.21g of 0.52~0.055g of L-threonine and citric acid, it is ultrapure water-soluble with 10mL Solution, pH are stirred at room temperature and ultrasound are transferred in the reaction kettle of polytetrafluoroethylene (PTFE) to after dissolving completely under conditions of 6.8~7.1; Temperature of reaction kettle is adjusted to keeping 1~12h, cooled to room temperature after 160~180 DEG C, and reaction solution is packed into bag filter and (is cut Stay relative molecular mass 1000) in, dialyzate is deionized water, and dialysis time is 48~96h, is lyophilized to obtain the final product.
In the present application content and preferred embodiment, the carbon dots (CDs-Thr) of the water-soluble doping threonine are classes Spherical nano particle, particle diameter distribution is within the scope of 1.0~3.0nm.
The application is using L-threonine and the citric acid particle diameter distribution spherical as Material synthesis class in 1.0~3.0nm range Interior CDs-Thr nano particle, as depicted in figs. 1 and 2, the good biocompatibility of CDs-Thr nano particle, highly concentrated Still without apparent killing functions of immunocytes in the case of degree, cellular machinery will not be caused obviously to damage, with traditional quantum dot phase Than with lower bio-toxicity, more conducively biological culture, bioanalysis, cell marking and in terms of research And application;Especially it is noted that in this application, being irradiated using the blue light that CDs-Thr nano particle combines 440~460nm Sargassum thunbergii is cultivated, the sargassum thunbergii liquid making that there is larger adsorption capacity to heavy metal ion can be obtained, can be effectively removed Cu in polluted-water2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations heavy metal ion, can use extensively In the treatment process of contaminant water, waste water etc., it is with a wide range of applications.
[2] a kind of compound sargassum thunbergii preparation for quickly removing heavy metal ion in polluted-water comprising:
The fresh sargassum thunbergii of -75~95wt% obtained by item [1] the method;
The fresh cyanobacteria of -5~25wt%;
The zinc salt of -0.1~1wt%;
PH adjusting agent.
In the present application content and preferred embodiment, the zinc salt is selected from inorganic acid zinc salt such as zinc chloride, zinc sulfate, nitre At least one of sour zinc and zinc salts of organic acid such as zinc gluconate, zinc citrate.
The pH adjusting agent is selected from quick lime, white lime, carbon dioxide, sulfuric acid and hydrochloric acid.
The application is multiple using the fresh sargassum thunbergii and fresh cyanobacteria and zinc salt, pH adjusting agent obtained by item [1] the method The compound sargassum thunbergii preparation of heavy metal ion in quickly removal polluted-water is made into, it can be achieved that the huge sum of money such as mantoquita, mercury salt, lead salt The efficient absorption of category can effectively remove the Cu in polluted-water2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or a variety of groups Heavy metal ion is closed, can be widely applied to the treatment process of contaminant water, waste water etc..
[3] a kind of method using heavy metal ion in sargassum thunbergii removal polluted-water comprising:
1) item [2] described compound sargassum thunbergii preparation is put into target stains water body;
2) being filled with 12~36h of air stirring is fully absorbed the heavy metal ion in target stains water body;
Wherein, the heavy metal ion is Cu2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations.
The invention has the benefit that
1) sargassum thunbergii cultural method step provided by the invention is simple, easily operated, and the speed of growth of sargassum thunbergii is fast, nutrition Photosynthetic matter accumulation amount is big, while being also used as the former material of the heavy mental treatment agent of heavy metal ion in removal polluted-water Material;
2) the application is using L-threonine and the citric acid particle diameter distribution spherical as Material synthesis class in 1.0~3.0nm model CDs-Thr nano particle in enclosing, the good biocompatibility of CDs-Thr nano particle, still in high concentration There is no apparent killing functions of immunocytes, cellular machinery will not be caused obviously to damage, has compared with traditional quantum dot lower Bio-toxicity, more conducively biological culture, bioanalysis, cell marking and in terms of research and application;
3) sargassum thunbergii is cultivated using the blue light irradiation that CDs-Thr nano particle combines 440~460nm, can be obtained The sargassum thunbergii liquid making that there is larger adsorption capacity to heavy metal ion is obtained, is with a wide range of applications;
4) it is re-dubbed using the fresh sargassum thunbergii obtained by herein described method with fresh cyanobacteria and zinc salt, pH adjusting agent The compound sargassum thunbergii preparation of heavy metal ion in polluted-water is quickly removed, it can be achieved that heavy metals such as mantoquita, mercury salt, lead salts Efficient absorption can effectively remove the Cu in polluted-water2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations weight Metal ion can be widely applied to the treatment process of contaminant water, waste water etc..
Present invention employs above-mentioned technical proposals to provide model essay, compensates for the deficiencies in the prior art, design is reasonable, operation side Just.
Detailed description of the invention
For above and other purpose, feature, advantage and embodiment of the invention can be clearer and more comprehensible, appended attached drawing is said It is bright as follows:
Fig. 1 is the preparation process schematic diagram of the carbon dots of water-soluble doping threonine of the invention;
Fig. 2 is the partial size schematic diagram of the carbon dots of the water-soluble doping threonine in the embodiment of the present invention 1.
Specific embodiment
Unless otherwise defined, technical and scientific term used herein has ordinary skill of the art The identical meaning that personnel are generally understood.The present invention uses method described herein and material;But as is generally known in the art Other suitable methods and material can also be used.Material, method and example described herein are merely illustrative, It is not intended for limiting.All publications, patent application case, Patent Case, Provisional Application, data base entries and herein Other bibliography referred to etc., entirety is incorporated herein as reference.It include being defined as with this specification if there is conflict It is quasi-.
A kind of sargassum thunbergii cultural method comprising:
1) algae basis is cultivated: being cultivated the sargassum thunbergii cell inoculation after activation to basis with 0.1 Initial seeding density In base, culture to logarithmic growth phase;
2) it algae optimization culture: takes and is cultivated in step 1) to the rat-tail algae solution of logarithmic growth phase, through centrifugation or filtration washing After obtain algal gel, the nitrogen source being inoculated with into another addition N doping carbon dots is reduced basal medium, and culture is to stabilization under blue light irradiation Phase harvests frustule;
Wherein, the N doping carbon dots are the carbon dots (CDs-Thr) of water-soluble doping threonine;
The intensity of illumination of the blue light irradiation is 1500~2500Lux, and the wavelength of blue light is 440~460nm.
Herein described sargassum thunbergii cultural method includes following limitations:
A) the basal medium composition in the algae basis incubation step of step 1) is as follows: 11.0~15.0g/ of sodium bicarbonate L, 0.5~1.0g/L of dipotassium hydrogen phosphate, 3.2~5.2g/L of calcium nitrate, 3.2~4.0g/L of sodium chloride, 0.12~0.2g/ of magnesium sulfate L, 0.01~0.20g/L of ferrous sulfate, 1.25~1.5mg/L of boric acid, 2.5~5.0mg/L of zinc sulfate, copper sulphate 3.0~ 10.0mg/L, 2.0~3.0mg/L of cobalt nitrate, remaining is water, pH value 7.0~7.5;
B) cultivation temperature in the algae basis incubation step of step 1) is 25~32 DEG C, and 12L/12D is with intensity of illumination 3000~4000Lux irradiation;
C) the addition N doping carbon dots of step 1) nitrogen source decrement basal medium be in basal medium addition 55~ The carbon dots of the water-soluble doping threonine of 100mg/L, and the content of calcium nitrate is adjusted to 1.2~1.5g/L;
D) in step 2), algal gel is directly diluted to through the nitrogen source decrement basal medium of another addition N doping carbon dots and initially connects Kind density is 0.25~0.35;
E) cultivation temperature of the algae optimization culture of step 2) is 30~32 DEG C, and pH is 7.0~8.0;
F) carbon dots of the water-soluble doping threonine of step 2) the preparation method comprises the following steps: weighing 0.52~0.055g of L-threonine It with 0.20~0.21g of citric acid, is dissolved with 10mL ultrapure water, pH is to be stirred at room temperature and ultrasound is to molten under conditions of 6.8~7.1 It is transferred in the reaction kettle of polytetrafluoroethylene (PTFE) after solution is complete;Temperature of reaction kettle is adjusted to keeping 1~12h after 160~180 DEG C, from It is so cooled to room temperature, and reaction solution is fitted into bag filter (retention relative molecular mass 1000), dialyzate is deionized water, thoroughly The analysis time is 48~96h, is lyophilized to obtain the final product;
G) carbon dots of the water-soluble doping threonine are spherical nano particles, and particle diameter distribution is in 1.0~3.0nm model In enclosing.
The application is using L-threonine and the citric acid particle diameter distribution spherical as Material synthesis class in 1.0~3.0nm range Interior CDs-Thr nano particle, the good biocompatibility of CDs-Thr nano particle, does not still have in high concentration There is apparent killing functions of immunocytes, cellular machinery will not be caused obviously to damage, there is lower life compared with traditional quantum dot Object toxicity, more conducively biological culture, bioanalysis, cell marking and in terms of research and application;Especially need , it is noted that in this application, being trained using the blue light irradiation that CDs-Thr nano particle combines 440~460nm to sargassum thunbergii It supports, the sargassum thunbergii liquid making that there is larger adsorption capacity to heavy metal ion can be obtained, the Cu in polluted-water can be effectively removed2 +、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations heavy metal ion, can be widely applied to contaminant water, waste water etc. Treatment process, be with a wide range of applications.
The compound sargassum thunbergii preparation of heavy metal ion in a kind of quick removal polluted-water comprising:
The fresh sargassum thunbergii of -75~95wt% obtained by method described above;
The fresh cyanobacteria of -5~25wt%;
The zinc salt of -0.1~1wt%;
PH adjusting agent.
Herein described compound sargassum thunbergii preparation includes subordinate's limitation:
A) zinc salt is selected from inorganic acid zinc salt such as zinc chloride, zinc sulfate, zinc nitrate and zinc salts of organic acid such as glucose At least one of sour zinc, zinc citrate;
B) pH adjusting agent described in is selected from quick lime, white lime, carbon dioxide, sulfuric acid and hydrochloric acid.
The application is used and is compounded by the fresh sargassum thunbergii that aforementioned the method obtains with fresh cyanobacteria and zinc salt, pH adjusting agent At the compound sargassum thunbergii preparation of heavy metal ion in quick removal polluted-water, it can be achieved that heavy metals such as mantoquita, mercury salt, lead salts Efficient absorption, the Cu in polluted-water can be effectively removed2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations Heavy metal ion can be widely applied to the treatment process of contaminant water, waste water etc..
A method of utilizing heavy metal ion in sargassum thunbergii removal polluted-water comprising:
1) compound sargassum thunbergii preparation described above is put into target stains water body;
2) being filled with 12~36h of air stirring is fully absorbed the heavy metal ion in target stains water body;
Wherein, the heavy metal ion is Cu2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations.
Embodiment 1:
The present embodiment provides a kind of sargassum thunbergii cultural methods comprising:
1) algae basis is cultivated: being cultivated the sargassum thunbergii cell inoculation after activation to basis with 0.1 Initial seeding density In base, culture to logarithmic growth phase;
2) it algae optimization culture: takes and is cultivated in step 1) to the rat-tail algae solution of logarithmic growth phase, through centrifugation or filtration washing After obtain algal gel, the nitrogen source being inoculated with into another addition N doping carbon dots is reduced basal medium, and culture is to stabilization under blue light irradiation Phase harvests frustule;
Wherein, the N doping carbon dots are the carbon dots (CDs-Thr) of water-soluble doping threonine;
The intensity of illumination of the blue light irradiation is 2000Lux, and the wavelength of blue light is 440~460nm.
Specifically, sargassum thunbergii cultural method described in the present embodiment includes following limitations:
A) the basal medium composition in the algae basis incubation step of step 1) is as follows: sodium bicarbonate 13.5g/L, phosphoric acid Hydrogen dipotassium 0.8g/L, calcium nitrate 4.0g/L, sodium chloride 3.5g/L, magnesium sulfate 0.15g/L, ferrous sulfate 0.1g/L, boric acid 1.5mg/L, zinc sulfate 3.0mg/L, copper sulphate 5.0mg/L, cobalt nitrate 2.5mg/L, remaining is water, pH value 7.0;
B) cultivation temperature in the algae basis incubation step of step 1) is 30 DEG C, and 12L/12D is with intensity of illumination 3500Lux Irradiation;
C) the nitrogen source decrement basal medium of the addition N doping carbon dots of step 1) is that 80mg/ is added in basal medium The carbon dots of the water-soluble doping threonine of L, and the content of calcium nitrate is adjusted to 1.4g/L;
D) in step 2), algal gel is directly diluted to through the nitrogen source decrement basal medium of another addition N doping carbon dots and initially connects Kind density is 0.25;
E) cultivation temperature of the algae optimization culture of step 2) is 32 DEG C, and pH is 7.2;
F) carbon dots of the water-soluble doping threonine of step 2) the preparation method comprises the following steps: weighing L-threonine 0.542g and lemon Sour 0.21g is dissolved with 10mL ultrapure water, and pH is stirred at room temperature and ultrasound is transferred to poly- four to after dissolving completely under conditions of 7.0 In the reaction kettle of vinyl fluoride;Temperature of reaction kettle is adjusted to keeping 6h, cooled to room temperature after 180 DEG C, and reaction solution is packed into In bag filter (retention relative molecular mass 1000), dialyzate is deionized water, and dialysis time 72h is lyophilized to obtain the final product;
G) carbon dots of the water-soluble doping threonine are spherical nano particles, and particle diameter distribution is in 1.0~3.0nm model In enclosing, as shown in Figure 2.
The application is using L-threonine and the citric acid particle diameter distribution spherical as Material synthesis class in 1.0~3.0nm range Interior CDs-Thr nano particle, the good biocompatibility of CDs-Thr nano particle, does not still have in high concentration There is apparent killing functions of immunocytes, cellular machinery will not be caused obviously to damage, there is lower life compared with traditional quantum dot Object toxicity, more conducively biological culture, bioanalysis, cell marking and in terms of research and application;Especially need , it is noted that in this application, being trained using the blue light irradiation that CDs-Thr nano particle combines 440~460nm to sargassum thunbergii It supports, the sargassum thunbergii liquid making that there is larger adsorption capacity to heavy metal ion can be obtained, the Cu in polluted-water can be effectively removed2 +、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations heavy metal ion, can be widely applied to contaminant water, waste water etc. Treatment process, be with a wide range of applications.
Embodiment 2:
The present embodiment provides a kind of compound sargassum thunbergii preparations of heavy metal ion in quickly removal polluted-water comprising:
The fresh sargassum thunbergii of -90.0wt% obtained by 1 the method for embodiment;
The fresh cyanobacteria of -9.0wt%;
The zinc salt of -1.0wt%;
PH adjusting agent.
Compound sargassum thunbergii preparation described in the present embodiment includes subordinate's limitation:
A) zinc salt is zinc sulfate;
B) pH adjusting agent described in is white lime and hydrochloric acid.
Embodiment 3:
The present embodiment provides a kind of methods using heavy metal ion in sargassum thunbergii removal polluted-water, comprising:
1) compound sargassum thunbergii preparation described in embodiment 2 is put into target stains water body;
2) being filled with air stirring for 24 hours is fully absorbed the heavy metal ion in target stains water body;
Wherein, the heavy metal ion is Cu2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations.
Comparative example D4:
Comparative example D4 is substantially the same manner as Example 1, difference from example 1 is that algae optimization culture step The nitrogen source of N doping carbon dots is not added in basal medium, the nitric acid calcium content in basal medium is not reduced;Subsequent foundation is real The method for applying example 2 compounds compound sargassum thunbergii preparation, is gone using the compound sargassum thunbergii preparation of this example preparation according to the method for embodiment 3 Depollution Heavy Metals in Waters ion.
Comparative example D5:
Comparative example D5 is substantially the same manner as Example 1, difference from example 1 is that algae optimization culture step Blue light irradiation is white light irradiation;The subsequent method according to embodiment 2 compounds compound sargassum thunbergii preparation, utilizes the compound of this example preparation Sargassum thunbergii preparation is according to heavy metal ion in the method removal polluted-water of embodiment 3.
Comparative example D6:
Comparative example D6 is substantially the same manner as Example 1, difference from example 1 is that algae optimization culture step The nitrogen source for the N doping carbon dots added in basal medium is using Pidolidone and citric acid as the CDs-Glu of Material synthesis nanometer Particle, and with the subsequent method culture sargassum thunbergii of embodiment 1;The subsequent method according to embodiment 2 compounds compound sargassum thunbergii system Agent, using the compound sargassum thunbergii preparation of this example preparation according to heavy metal ion in the method removal polluted-water of embodiment 3.
Comparative example D7:
Comparative example D7 and comparative example D6 are essentially identical, with comparative example D6 the difference is that replacing L- with L-lysine Glutamic acid prepare CDs-Lys nano particle, and with the subsequent method culture sargassum thunbergii of embodiment 1;Subsequent foundation embodiment 2 Method compounds compound sargassum thunbergii preparation, removes depollution according to the method for embodiment 3 using the compound sargassum thunbergii preparation of this example preparation Heavy Metals in Waters ion.
Comparative example D8:
Comparative example D8 is substantially the same manner as Example 2, with embodiment 2 the difference is that compound sargassum thunbergii preparation packet It includes:
The fresh sargassum thunbergii of -99.0wt% obtained by 1 the method for embodiment;
The zinc salt of -1.0wt%;
PH adjusting agent.
Using this example preparation compound sargassum thunbergii preparation according to embodiment 3 method removal polluted-water in heavy metal from Son.
Comparative example D9:
Comparative example D9 is substantially the same manner as Example 2, with embodiment 2 the difference is that compound sargassum thunbergii preparation, Include:
The fresh sargassum thunbergii of -90.0wt% obtained by 1 the method for embodiment;
The fresh cyanobacteria of -10.0wt%;
PH adjusting agent.
Using this example preparation compound sargassum thunbergii preparation according to embodiment 3 method removal polluted-water in heavy metal from Son.
Experimental example:
Target stains water body in embodiment 3 and comparative example D4~D9 is consistent, is counted before each example processing respectively and processing The content of each heavy metal ion in water body afterwards, and removal of the compound sargassum thunbergii preparation of each example to each heavy metal ion is calculated Effect, statistical result are as shown in table 1.
Table 1, compound sargassum thunbergii preparation are to the removal effect of heavy metal ion
As shown in Table 1, if whether cultivated with the culture medium of the nitrogen source containing N doping carbon dots and with blue light irradiation Obtained sargassum thunbergii is larger to the function influence of heavy metal ion in final removal polluted-water, it can be seen that amino acid source is not It is smaller with the influence to final heavy-metal ion removal, it is whether same as zinc salt to removal containing cyanobacteria in compound sargassum thunbergii preparation The effect of heavy metal ion has larger impact in polluted-water, it is known that the present processes can effectively remove in polluted-water Cu2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6+One of or multiple combinations heavy metal ion, can be widely applied to contaminant water, waste water Deng treatment process.
The prior art of routine techniques dawn known to those skilled in the art in above-described embodiment, therefore herein no longer in detail It repeats.
Although above-mentioned specific embodiment has shown that, is described and pointed out novel feature applied to various embodiments, It, can form and details to illustrated device or method it should be understood that under the premise of not departing from the spirit of present disclosure Carry out various omissions, substitutions and changes.In addition, above-mentioned various features and method can be used independently of each other, or can be with various sides Formula combination.All possible combination and sub-portfolio are intended to and fall within the scope of the present disclosure.Above-mentioned many embodiment packets Similar component is included, and therefore, these similar components are interchangeable in different implementation scenarios.Although in certain realities Apply scheme and embodiment it is disclosed in the context that the present invention, it is understood by one skilled in the art that the present invention can be beyond specific Disclosed embodiment extends to other alternate embodiments and/or application and its apparent modification and equivalent.Therefore, The present invention is not intended to be limited by the specific disclosure of this paper preferred embodiment.

Claims (10)

1. a kind of sargassum thunbergii cultural method, characterized by comprising:
1) algae basis cultivate: with 0.1 Initial seeding density by the sargassum thunbergii cell inoculation after activation into basal medium, It cultivates to logarithmic growth phase;
2) algae optimization culture: culture in step 1) is taken to obtain after centrifugation or filtration washing to the rat-tail algae solution of logarithmic growth phase To algal gel, the nitrogen source being inoculated with into another addition N doping carbon dots is reduced basal medium, and culture to stationary phase receives under blue light irradiation Obtain frustule;
Wherein, the N doping carbon dots are the carbon dots (CDs-Thr) of water-soluble doping threonine;
The intensity of illumination of the blue light irradiation is 1500~2500Lux, and the wavelength of blue light is 440~460nm.
2. according to the method described in claim 1, it is characterized by: the carbon dots (CDs-Thr) of the water-soluble doping threonine It is spherical nano particle, particle diameter distribution is within the scope of 1.0~3.0nm.
3. method according to claim 1 or 2, it is characterised in that: in the algae basis incubation step of the step 1) Cultivation temperature is 25~32 DEG C, and 12L/12D is with 3000~4000Lux of intensity of illumination irradiation.
4. method according to claim 1 or 2, it is characterised in that: the nitrogen source of the addition N doping carbon dots of the step 1) Decrement basal medium is the carbon dots (CDs- that the water-soluble doping threonine of 55~100mg/L is added in basal medium Thr it), and by the content of calcium nitrate adjusts to 1.2~1.5g/L.
5. method according to claim 1 or 2, it is characterised in that: in the step 2), algal gel is through another addition nitrogen-doped carbon It is 0.25~0.35 that the nitrogen source decrement basal medium of point, which is directly diluted to Initial seeding density,.
6. method according to claim 1 or 2, it is characterised in that: the carbon of the water-soluble doping threonine of the step 2) Point the preparation method comprises the following steps: weigh 0.20~0.21g of 0.52~0.055g of L-threonine and citric acid, dissolved with 10mL ultrapure water, PH is stirred at room temperature and ultrasound is transferred in the reaction kettle of polytetrafluoroethylene (PTFE) to after dissolving completely under conditions of 6.8~7.1;It adjusts Temperature of reaction kettle is saved to keeping 1~12h, cooled to room temperature after 160~180 DEG C, and reaction solution is packed into bag filter (retention Relative molecular mass 1000) in, dialyzate is deionized water, and dialysis time is 48~96h, is lyophilized to obtain the final product.
7. the compound sargassum thunbergii preparation of heavy metal ion in a kind of quickly removal polluted-water, characterized by comprising:
The fresh sargassum thunbergii of -75~95wt% obtained by any one of claim 1~6 the method;
The fresh cyanobacteria of -5~25wt%;
The zinc salt of -0.1~1wt%;
PH adjusting agent.
8. compound sargassum thunbergii preparation according to claim 7, it is characterised in that: the zinc salt is selected from inorganic acid zinc salt such as chlorine Change at least one of zinc, zinc sulfate, zinc nitrate and zinc salts of organic acid such as zinc gluconate, zinc citrate.
9. a kind of method using heavy metal ion in sargassum thunbergii removal polluted-water, characterized by comprising:
1) the compound sargassum thunbergii preparation of claim 7 or 8 is put into target stains water body;
2) being filled with 12~36h of air stirring is fully absorbed the heavy metal ion in target stains water body.
10. according to the method described in claim 9, it is characterized in that heavy metal ion is Cu2+、Hg2+、Cd2+、Pb2+、Ni2+、Cr6 +One of or multiple combinations.
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