CN106745592B - It is a kind of with heavy metal ion adsorbed and detection function composite flocculation agent and preparation method thereof - Google Patents
It is a kind of with heavy metal ion adsorbed and detection function composite flocculation agent and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention discloses a kind of with heavy metal ion adsorbed and detection function composite flocculation agent and preparation method thereof, belongs to polymeric material field.Product of the present invention is it is characterized in that not only can be effectively removed organic pollutants, but also can adsorb and detect the heavy metal ion such as nickel, chromium, lead in water, and good to heavy metal ion qualitative detection effect in water, and heavy metal ion adsorbed amount is big, adsorption efficiency is high.Product of the present invention reaches 90% or more to the eliminating rate of absorption of low-concentration heavy metal ions in waste water.Product of the present invention preparation does not need special installation, industrializing implementation is easy, and composite flocculation agent reduces the dosage of chitosan, reduces costs.
Description
Technical field
The present invention relates to polymeric material fields, and in particular to the heavy metal ion such as a kind of pair of nickel, chromium, lead have good inhale
Echo the composite flocculation agent preparation method of detection function.Organic pollutants both can be effectively removed in the composite flocculation agent,
The heavy metal ion such as nickel, chromium, lead, the mercury in water can be adsorbed and detect again, and, absorption big to amount heavy metal ion adsorbed in water
It is high-efficient, it can be applied to the process field of the sewage such as electroplating industry, chemical industry.
Background technique
In recent years, the random row of industrial wastewater leaves about, municipal refuse, rural area pesticide spraying etc. cause water pollution serious, especially
It is that Heavy Metals in Waters ion contamination problems are very prominent.In order to administer water pollution, the mankind explore numerous physics, chemistry
Method, flocculant are exactly maximum one kind of dosage in chemical method water treatment agent, and effect can be produced to suspended particulates in water
Raw absorption, " bridge formation " achieve the purpose that accelerate sedimentation so that it be made to be agglomerated into coarse particle or floc sedimentation.
But flocculant industrial at present is not ideal enough to the treatment effect of heavy metal ions in wastewater, and heavy metal
Contaminated wastewater has become the serious social concern in China, is economic development and Environmental Health in the urgent need to address at present, drinking-water
The crucial problem of secure context.Currently, the method for removing heavy metal ions in wastewater mainly has: chemical precipitation and reduction, biology
With plant absorption, solvent extraction and membrane separation technique etc..
In recent years, inorganic material is to the absorption property of heavy metal ion increasingly by the concern of researcher, Duo Shuowu
Machine mineral material low cost and obvious to the absorption property of heavy metal ion, especially induces one at heavy metal ion adsorbed aspect
Note that wherein attapulgite is most typical a kind of.Attapulgite (also known as palygorskite) is a kind of natural non-metallic minerals
Material is a kind of aqueous rich magnesium silicate clay mineral with chain layer structure, typical chemical formula Si8Mg6O20(OH)2
(OH2)4·4H2O, structure belongs to 2:1 type clay mineral, and in each 2:1 unit structure layer, tetrahedron chip angle is pushed up every a spacing
Reverse, the forming layer chain from direction.The special construction of attapulgite makes it have very big specific surface area, and physical absorption ability is very
By force.On the other hand, attapulgite has level negative electrical charge, in cation of the Inter layer adsorption with interchangeability so that charge is flat
Weighing apparatus, such attapulgite are just provided with stronger ionic adsorption exchange capacity.
The present inventor discloses the preparation method and its production of a kind of absorbent-type macromolecule composite hydrogel in invention early period
Product (ZL201020595998.1) make carrier, immobilized attapulgite, to play concave convex rod well using macromolecule hydrogel
The suction-operated of soil.In addition, disclosing a kind of chitin composite flocculant big to heavy metal ion adsorbed amount, adsorption efficiency is high
Preparation method and products thereof (CN103274509A).The present inventor also discloses absorption heavy metal ion in invention early period
PVDF hybrid flat [ZL201110254106.0], using plate membrane as carrier, immobilized attapulgite has played recessed well
Suction-operated of the convex stick soil to heavy metal ion.
But how attapulgite to be applied in sewage treatment, organic pollutants not only can be effectively removed, but also
It can be still a great problem with the heavy metal ion in efficient absorption water.In addition, attapulgite is used for heavy metal ion adsorbed material
Material, only has single heavy metal ion adsorbed function, cannot detect simultaneously to heavy metal ion.One kind is designed both to have
Good absorption property again can adsorbent material existing for field quick detection heavy metal be still a challenge.
Carbon quantum dot (CD) is non-toxic or low-toxic, molecular weight is low, partial size is small, cheap, with very peculiar chemistry and
Physical property and possess strong fluorescence, water solubility and biocompatibility etc., can be applied to bio-imaging, medical diagnosis, urges
In agent, photovoltaic device, while the characteristic for being easy to be quenched by metal ion causes the very big concern of researchers in recent years, to
To in the detection application of heavy metal ion.Gogoi N etc. mixes chitosan carbon dots solution with gelatin solution, microwave molding, preparation
Gelatin/carbon dots hybrid flat out, have studied separation to heavy metal and detection performance [Gogoi N, Barooah M,
Majumdar G,et al.Carbon dots rooted agarose hydrogel hybrid platform for
optical detection and separation of heavy metal ions[J].ACS applied
materials&interfaces,2015,7(5):3058-3067.].But it on the whole, explores while having in water treatment field
The standby material for adsorbing and detecting heavy metal ion is not much, i.e., before absorption and tluorimetric composite material have very big application
Scape.
Summary of the invention
It is not ideal enough to the treatment effect of heavy metal ions in wastewater for existing industrial flocculant, and tradition Xu
The technical issues of gel deficiency existing for heavy metal ion adsorbed and context of detection, the present invention intends to solve, which is to provide one kind, to be had
Adsorb and monitor simultaneously the preparation method of the composite flocculation agent of heavy metal ion.The composite flocculation agent is a kind of chitosan/bumps
Stick soil/carbon dots composite flocculation agent can both play traditional flocculant effect, and effectively remove organic pollutants, and can
To adsorb and detect the heavy metal ion such as the nickel in water, chromium, lead, and a, huge sum of money good to heavy metal ion qualitative detection effect in water
Category ionic adsorption amount is big, adsorption efficiency is high.
Product of the present invention uses chitosan for raw material, attapulgite modified to prepare for modifying agent with glutaraldehyde as cross linker
It obtains.Product of the present invention uses commercially available carbon dots, with coupling agent 3- glycidyloxypropyl trimethoxy silane
(KH560) it is modified processing to it, prepares the modified carbon dots of KH560.
It is of the present invention that there is heavy metal ion adsorbed and detection function composite flocculation agent to be made by following methods:
(1) pretreatment of attapulgite.300 mesh of 10g~20g partial size~1000 mesh attapulgite is weighed, is distilled with 1L
Water washing takes its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugation 1min, a small amount of distillation is added in supernatant liquor after to be precipitated
Water continues 500rpm centrifugation 1min after mixing, then takes its supernatant liquor, after washing supernatant liquor 3~5 times repeatedly,
It is finally centrifuged with 4000rpm, takes its precipitating, be dried in vacuo at 90 DEG C for 24 hours, corresponded to after grinding by particle size selection
The sieve of mesh number obtains purifying attapulgite.
Configuration concentration is the hydrochloric acid solution of 0.5mol/L~3mol/L, take 10g~20g purifying attapulgite and 150mL~
200mL hydrochloric acid solution, which is added in small beaker, to be stirred, and after 5min, heats the mixture to 70 DEG C~80 DEG C, and stirring 1h~
2h, then sonic oscillation 30min~40min, filters, and being washed with distilled water to pH is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C,
The sieve for selecting corresponding mesh number after grinding by particle size, obtains sour attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 4:1~5:1) is added the acetum that 100ml concentration is 1%~2% and stirs, after completely dissolution to it, use
The NaOH solution of 1mol/L adjusts pH to 10, is added 20ml~30ml glutaraldehyde cross-linking 3h~5h (60 DEG C of water-baths are vigorously stirred).
Flocculant after crosslinking is filtered, distillation is washed to neutrality, up to of the present invention compound after 50 DEG C~70 DEG C vacuum drying
Flocculant.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 1~5mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is CD
The 5%~20% of liquor capacity.15~30h of uniform stirring at 20 DEG C~50 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
It is prepared to calculate the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 1%~5% for composite flocculation agent
CD-KH560 solution, flocculant is immersed in CD-KH560 solution, concussion 6h~for 24 hours, institute are protected from light in 20 DEG C~40 DEG C shaking tables
Product distillation washing be freeze-dried afterwards three times the chitosan that there is heavy metal ion adsorbed and detection function to get the present invention/
Attapulgite/carbon dots composite flocculation agent.
Beneficial effect
The composite flocculation agent that the present invention solves the absorption heavy metal ion is attapulgite modified multiple using chitosan and acid
Conjunction is prepared.Chitosan is chitin deacetylation product, is used as flocculant, and organic dirt in water can be effectively removed
Object is contaminated, and there is good flocculating property in an acidic solution.Attapulgite be a kind of abundance, inexpensive, heavy metal from
The inorganic mineral of sub- excellent adsorption can adsorb the heavy metal ion in water with its flocculant prepared simultaneously.Therefore, this item
The composite flocculation agent of mesh preparation can play the advantage of chitosan and attapulgite respectively, cooperate with its flocculation, improve compound
The scope of application and flocculation efficiency of flocculant.In addition, chitosan/attapulgite clay compounded flocculant reduces the dosage of chitosan,
It reduces costs.
It is the composite flocculation agent of monitoring and heavy-metal ion removal prepared by the present invention, is connect using being blended with surface
Branch method, which can adsorb and monitor simultaneously heavy metal ion, and heavy metal ion adsorbed property is excellent, and fluorescence is quenched
Going out property is prominent.Decrease or quenching effect is presented in composite flocculation agent product of the present invention fluorescence in heavy metal ion solution, this
Kind responsiveness can reach real-time monitoring purpose to water quality.Composite flocculation agent product of the present invention is to low concentration nickel, chromium, lead, mercury
Etc. the eliminating rate of absorption of heavy metal ion reach 90% or more.Therefore, product of the present invention not only has heavy metal ion excellent
Removal effect, moreover it is possible to have real-time monitoring effect to the heavy metal ion in water quality.
Compared with prior art, composite flocculation agent preparation method of the present invention has simple process, does not need special installation, work
Industryization is implemented to be easy.Product of the present invention technology chitosan has biggish covering amount to attapulgite, so that product cost is low, and
Storeroom compatibility is good.
Specific embodiment
The following examples can make those skilled in the art that the present invention be more fully understood, but not limit in any way
The present invention
Embodiment 1
(1) pretreatment of attapulgite.The attapulgite for weighing 300 mesh of 10g partial size distills water washing with 1L, to be precipitated
After take its supernatant liquor, take its supernatant liquor after 500rpm centrifugation 1min, in supernatant liquor plus a small amount of distilled water after mixing
Continue 500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 3 times after, finally with 4000rpm into
Row centrifuge separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size,
Attapulgite must be purified.
Configuration concentration is the hydrochloric acid solution of 0.5mol/L, takes 10g purifying attapulgite to be added to 150mL hydrochloric acid solution small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, with distillation
Water washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size,
It obtains sour attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 4:1) is added the acetum that 100ml concentration is 1% and stirs, after completely dissolution to it, use the NaOH of 1mol/L
Solution adjusts pH to 10, is added 20ml glutaraldehyde cross-linking 3h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is filtered, is steamed
Distilled water is washed till neutrality, up to composite flocculation agent of the present invention after 50 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 1mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is that CD is molten
The 5% of liquid product.Uniform stirring 15h at 20 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent calculates CD- prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 1%
KH560 solution immerses flocculant in CD-KH560 solution, and concussion 6h, products therefrom distillation washing three are protected from light in 20 DEG C of shaking tables
Freeze-drying has heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots compound after secondary to get the present invention
Flocculant.
Embodiment 2
(1) pretreatment of attapulgite.The attapulgite for weighing 1000 mesh of 10g partial size distills water washing with 1L, and precipitating takes
Its supernatant liquor, 500rpm take its supernatant liquor after being centrifuged 1min, add a small amount of distilled water to continue after mixing in supernatant liquor
500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 3 times after, finally with 4000rpm carry out from
Heart separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 0.5mol/L, takes 20g purifying attapulgite to be added to 150mL hydrochloric acid solution small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, with distillation
Water washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size,
It obtains sour attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 4:1) is added the acetum that 100ml concentration is 2% and stirs, after completely dissolution to it, use the NaOH of 1mol/L
Solution adjusts pH to 10, is added 20ml glutaraldehyde cross-linking 3h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is filtered, is steamed
Distilled water is washed till neutrality, up to composite flocculation agent of the present invention after 50 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 2mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is that CD is molten
The 8% of liquid product.Uniform stirring 15h at 20 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent calculates CD- prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 2%
KH560 solution immerses flocculant in CD-KH560 solution, and concussion 12h, products therefrom distillation washing three are protected from light in 30 DEG C of shaking tables
Freeze-drying has heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots compound after secondary to get the present invention
Flocculant.
Embodiment 3
(1) pretreatment of attapulgite.The attapulgite for weighing 300 mesh of 20g partial size distills water washing with 1L, and precipitating takes
Its supernatant liquor, 500rpm take its supernatant liquor after being centrifuged 1min, add a small amount of distilled water to continue after mixing in supernatant liquor
500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 5 times after, finally with 4000rpm carry out from
Heart separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 3mol/L, and 10g purifying attapulgite and 150mL hydrochloric acid solution is taken to be added to small burning
It is stirred in cup, after 5min, heats the mixture to 80 DEG C, stir 2h, then sonic oscillation 30min, filter, use distilled water
Washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size, obtains
Acid is attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 5:1) is added the acetum that 100ml concentration is 2% and stirs, after completely dissolution to it, use the NaOH of 1mol/L
Solution adjusts pH to 10, is added 20ml glutaraldehyde cross-linking 5h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is filtered, is steamed
Distilled water is washed till neutrality, up to composite flocculation agent of the present invention after 70 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 5mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is that CD is molten
The 20% of liquid product.Uniform stirring 30h at 50 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent calculates CD- prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 3%
KH560 solution immerses flocculant in CD-KH560 solution, and concussion is protected from light in 40 DEG C of shaking tables for 24 hours, products therefrom distillation washing three
Freeze-drying has heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots compound after secondary to get the present invention
Flocculant.
Embodiment 4
(1) pretreatment of attapulgite.The attapulgite for weighing 500 mesh of 15g partial size distills water washing with 1L, and precipitating takes
Its supernatant liquor, 500rpm take its supernatant liquor after being centrifuged 1min, add a small amount of distilled water to continue after mixing in supernatant liquor
500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 5 times after, finally with 4000rpm carry out from
Heart separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 1mol/L, and 12g purifying attapulgite and 180mL hydrochloric acid solution is taken to be added to small burning
It is stirred in cup, after 5min, heats the mixture to 70 DEG C, stir 1h, then sonic oscillation 30min, filter, use distilled water
Washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size, obtains
Acid is attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 5:1) is added the acetum that 100ml concentration is 1.5% and stirs, after completely dissolution to it, use 1mol/L's
NaOH solution adjusts pH to 10, is added 30ml glutaraldehyde cross-linking 4h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, up to composite flocculation agent of the present invention after 60 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 4mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is that CD is molten
The 15% of liquid product.Uniform stirring 20h at 40 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent calculates CD- prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 4%
KH560 solution immerses flocculant in CD-KH560 solution, and concussion 30h, products therefrom distillation washing three are protected from light in 35 DEG C of shaking tables
Freeze-drying has heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots compound after secondary to get the present invention
Flocculant.
Embodiment 5
(1) pretreatment of attapulgite.The attapulgite for weighing 800 mesh of 16g partial size distills water washing with 1L, and precipitating takes
Its supernatant liquor, 500rpm take its supernatant liquor after being centrifuged 1min, add a small amount of distilled water to continue after mixing in supernatant liquor
500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 5 times after, finally with 4000rpm carry out from
Heart separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 2.5mol/L, takes 18g purifying attapulgite to be added to 160mL hydrochloric acid solution small
It is stirred in beaker, after 5min, heats the mixture to 70 DEG C, stir 2h, then sonic oscillation 40min, filter, with distillation
Water washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size,
It obtains sour attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 5:1) is added the acetum that 100ml concentration is 1.8% and stirs, after completely dissolution to it, use 1mol/L's
NaOH solution adjusts pH to 10, is added 25ml glutaraldehyde cross-linking 5h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, up to composite flocculation agent of the present invention after 70 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 5mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is that CD is molten
The 20% of liquid product.Uniform stirring for 24 hours, obtains CD-KH560 solution at 40 DEG C.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent calculates CD- prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 5%
KH560 solution immerses flocculant in CD-KH560 solution, and concussion is protected from light in 40 DEG C of shaking tables for 24 hours, products therefrom distillation washing three
Freeze-drying has heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots compound after secondary to get the present invention
Flocculant.
Embodiment 6
(1) pretreatment of attapulgite.The attapulgite for weighing 1000 mesh of 18g partial size distills water washing with 1L, and precipitating takes
Its supernatant liquor, 500rpm take its supernatant liquor after being centrifuged 1min, add a small amount of distilled water to continue after mixing in supernatant liquor
500rpm be centrifuged 1min, then take its supernatant liquor, repeatedly wash supernatant liquor 5 times after, finally with 4000rpm carry out from
Heart separation, takes its precipitating, is dried in vacuo at 90 DEG C for 24 hours, selects the sieve of corresponding mesh number after grinding by particle size, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 3mol/L, and 20g purifying attapulgite and 180mL hydrochloric acid solution is taken to be added to small burning
It is stirred in cup, after 5min, heats the mixture to 75 DEG C, stir 1.5h, then sonic oscillation 35min, filter, with distillation
Water washing is about to be dried in vacuo for 24 hours at 6 or so, 90 DEG C to pH, selects the sieve of corresponding mesh number after grinding by particle size,
It obtains sour attapulgite modified.
(2) preparation of chitin composite flocculant.4g chitosan is weighed to mix with a certain amount of modified attapulgite of acid
(mass ratio 4:1) is added the acetum that 100ml concentration is 1.6% and stirs, after completely dissolution to it, use 1mol/L's
NaOH solution adjusts pH to 10, is added 25ml glutaraldehyde cross-linking 4h (60 DEG C of water-baths are vigorously stirred).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, up to composite flocculation agent of the present invention after 60 DEG C of vacuum drying.
(3) preparation of the modified carbon dots of KH560.The CD solid for weighing certain mass, is dissolved in deionized water, is made into
Solution concentration is the CD solution of 3.8mg/mL.A certain amount of KH560 is added in carbon dots aqueous solution, the additive amount of KH560 is CD
The 18% of liquor capacity.Uniform stirring 30h at 36 DEG C, obtains CD-KH560 solution.
(4) chitosan/attapulgite/carbon dots composite flocculation agent preparation.Weigh chitosan prepared in 10mg step (2)
Composite flocculation agent is calculated prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 3.8%
CD-KH560 solution immerses flocculant in CD-KH560 solution, and concussion 20h, products therefrom distilled water are protected from light in 25 DEG C of shaking tables
It washes to be freeze-dried afterwards three times and there are heavy metal ion adsorbed and detection function chitosan/attapulgite/carbon dots to get the present invention
Composite flocculation agent.
Claims (2)
1. a kind of preparation method with heavy metal ion adsorbed and detection function composite flocculation agent, which is characterized in that including
Following steps:
(1) pretreatment of attapulgite: weighing 300 mesh of 10g~20g partial size~1000 mesh attapulgite, is distilled and is washed with 1L
It washs, its supernatant liquor is taken after to be precipitated, its supernatant liquor is taken after 500rpm centrifugation 1min, adds a small amount of distilled water mixed in supernatant liquor
Continue 500rpm after closing uniformly and be centrifuged 1min, then take its supernatant liquor, after washing supernatant liquor 3~5 times repeatedly, finally
It is centrifuged with 4000rpm, takes its precipitating, be dried in vacuo at 90 DEG C for 24 hours, select corresponding mesh number by particle size after grinding
Sieve, obtain purifying attapulgite；
Configuration concentration is the hydrochloric acid solution of 0.5mol/L~3mol/L, takes 10g~20g purifying attapulgite and 150mL~200mL
Hydrochloric acid solution is added in small beaker and is stirred, and after 5min, heats the mixture to 70 DEG C~80 DEG C, stirs 1h~2h, so
Sonic oscillation 30min~40min afterwards is filtered, and being washed with distilled water to pH is to be dried in vacuo for 24 hours at 6 or so, 90 DEG C, after grinding
The sieve that corresponding mesh number is selected by particle size, obtains sour attapulgite modified；
(2) 4g chitosan and a certain amount of modified attapulgite of acid the preparation of chitin composite flocculant: are weighed according to quality
It is mixed than 4:1 ~ 5:1, the acetum that 100ml concentration is 1% ~ 2% is added and stirs, after completely dissolution to it, uses 1mol/L's
NaOH solution adjusts pH to 10, and 20ml ~ 30ml glutaraldehyde is added and is crosslinked 3h ~ 5h under 60 DEG C of water-bath intense agitations；It will hand over
Flocculant after connection filters, and distillation is washed to neutrality, up to composite flocculation of the present invention after 50 DEG C ~ 70 DEG C vacuum drying
Agent；
(3) preparation of the modified carbon dots of 3- glycidyloxypropyl trimethoxy silane KH560: the carbon amounts of certain mass is weighed
Sub- point CD solid, is dissolved in deionized water, and wiring solution-forming concentration is the carbon quantum dot CD solution of 1 ~ 5mg/mL；Addition one
Quantitative 3- glycidyloxypropyl trimethoxy silane KH560 is in carbon dots aqueous solution, 3- glycidyl oxygroup third
The additive amount of base trimethoxy silane KH560 is the 5% ~ 20% of carbon quantum dot CD liquor capacity；Uniform stirring 15 at 20 DEG C ~ 50 DEG C
~ 30h obtains carbon quantum dot CD-3- glycidyloxypropyl trimethoxy silane KH560 solution；
(4) it is compound chitosan/attapulgite/carbon dots composite flocculation agent preparation: to weigh chitosan prepared in 10mg step (2)
Flocculant calculates carbon quantum prepared by the step of weighing certain volume (3) by the mass ratio of chitin composite flocculant 1% ~ 5%
Flocculant is immersed carbon quantum dot CD-3- and shunk by point CD-3- glycidyloxypropyl trimethoxy silane KH560 solution
In glyceryl oxygroup propyl trimethoxy silicane KH560 solution, concussion 6h ~ for 24 hours, products therefrom are protected from light in 20 DEG C ~ 40 DEG C shaking tables
Distillation washing is freeze-dried afterwards three times has heavy metal ion adsorbed and detection function chitosan/concave convex rod to get the present invention
Soil/carbon dots composite flocculation agent.
2. a kind of with heavy metal ion adsorbed and detection function composite flocculation agent, which is characterized in that as described in claim 1
The preparation method of composite flocculation agent with heavy metal ion adsorbed and detection function a kind of be prepared.
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| CN103382389A (en) * | 2013-07-11 | 2013-11-06 | 中山大学 | Fluorescent carbon quantum dot, its light-emitting polymer based composite material and preparation method |
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| CN103382389A (en) * | 2013-07-11 | 2013-11-06 | 中山大学 | Fluorescent carbon quantum dot, its light-emitting polymer based composite material and preparation method |
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