CN106745592A - 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
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- 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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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- 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"
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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, belong to polymeric material field.Product of the present invention can adsorb and detect the heavy metal ion such as nickel, chromium, lead in water it is characterized in that both can effectively remove organic pollutants again, 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 more than 90% to the eliminating rate of absorption of low-concentration heavy metal ions in waste water.Product of the present invention is prepared and does not need special installation, industrializing implementation easily, and composite flocculation agent reduces the consumption of shitosan, reduces cost.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of that there is good suction to heavy metal ion such as nickel, chromium, lead
Echo the composite flocculation agent preparation method of detection function.The composite flocculation agent both can effectively remove organic pollutants,
The heavy metal ion such as nickel, chromium, lead, mercury in water, and, absorption big to heavy metal ion adsorbed amount in water can be adsorbed and detected again
Efficiency high, can be applied to the process field of the sewage such as electroplating industry, chemical industry.
Background technology
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 is exactly a class of consumption maximum in chemical method water treatment agent, and its effect is that suspended particulates in water can be produced
Raw absorption, " bridge formation ", so that it is agglomerated into thick particle or floc sedimentation, reach the purpose for accelerating 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 turned into the serious social concern of China, is economic development in the urgent need to address at present and Environmental Health, drinking-water
The crucial problem of secure context.At present, 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, the absorption property of inorganic material heavy metal ion is increasingly paid close attention to by researcher, Duo Shuowu
The absorption property of machine mineral material low cost and heavy metal ion substantially, particularly induces one at heavy metal ion adsorbed aspect
Note, wherein attapulgite is most typical a kind of.Attapulgite (also known as palygorskite) is a kind of natural non-metallic mineral matter
Material, is a kind of clay mineral of magnesium silicate containing Shuifu County with chain layer structure, and typical chemical formula is Si8Mg6O20(OH)2
(OH2)4·4H2O, structure belongs to 2:1 type clay mineral, each 2:In 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 carries aspect negative electrical charge, and the cation with interchangeability in Inter layer adsorption is so that electric charge is flat
Weighing apparatus, such attapulgite is just provided with stronger ionic adsorption exchange capacity.
The present inventor discloses the preparation method and its product of a kind of absorbent-type macromolecule composite aquogel in early stage invention
Product (ZL201020595998.1), carrier, immobilized attapulgite, so as to play concave convex rod well are made using macromolecule hydrogel
The suction-operated of soil.In addition, disclosing a kind of chitin composite flocculant that heavy metal ionic adsorption amount is big, adsorption efficiency is high
Preparation method and products thereof (CN103274509A).The present inventor also discloses Adsorption of Heavy Metals ion in early stage invention
PVDF hybrid flats【ZL201110254106.0】, using flat board membrane as carrier, immobilized attapulgite has been played recessed well
The suction-operated of convex rod soil heavy metal ion.
But, how attapulgite is applied in sewage disposal, organic pollutants both can be effectively removed, and
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, it has single heavy metal ion adsorbed function, it is impossible to while heavy metal ion is detected.Design one kind both had
Good absorption property again can field quick detection heavy metal exist sorbing material be still one challenge.
Carbon quantum dot (CD) is nontoxic or low toxicity, molecular weight are low, particle diameter is small, cheap, with very peculiar chemistry and
Physical property and possess strong fluorescence, water-soluble and biocompatibility etc., can be applied to bio-imaging, medical diagnosis, urge
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, it is used to
In the detection application of heavy metal ion.Gogoi N etc. mix shitosan carbon dots solution with gelatin solution, microwave shaping, prepare
Go out gelatin/carbon point hybrid flat, have studied separation and the detection performance of heavy metal【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 on the whole, explored in water treatment field and had simultaneously
Standby to adsorb and detect that the material of heavy metal ion is also few, i.e. absorption and tluorimetric composite has very big application preceding
Scape.
The content 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 deficiency that gel exists in heavy metal ion adsorbed and context of detection, the technical problem that the present invention is intended to solve is to provide one kind to be had
The preparation method of the composite flocculation agent of heavy metal ion is adsorbed and monitored simultaneously.The composite flocculation agent is a kind of shitosan/concavo-convex
Rod soil/carbon point composite flocculation agent, it can both play traditional flocculant effect, effectively remove organic pollutants, again might be used
It is to 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, a huge sum of money
Category ionic adsorption amount is big, adsorption efficiency is high.
It is raw material that product of the present invention uses shitosan, attapulgite modified for prepared by modifying agent with glutaraldehyde as cross linker
Obtain.Product of the present invention uses commercially available carbon point, with coupling agent 3- glycidyloxypropyl trimethoxy silanes
(KH560) treatment is modified to it, KH560 carbon modifieds point is prepared.
It is of the present invention to be obtained by following methods with heavy metal ion adsorbed and detection function composite flocculation agent：
(1) pretreatment of attapulgite.The attapulgite of mesh~1000 mesh of 10g~20g particle diameters 300 is weighed, is distilled with 1L
Water washing, it is to be precipitated after take its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, in supernatant liquor plus a small amount of distillation
Continue 500rpm centrifugation 1min after water is well mixed, then take its supernatant liquor, after such cyclic washing supernatant liquor 3~5 times,
Finally it is centrifuged with 4000rpm, takes its precipitation, 24h is vacuum dried at 90 DEG C, correspondence is selected by particle size after grinding
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 solutions are added to and mixing are stirred in small beaker, after 5min, heat the mixture to 70 DEG C~80 DEG C, and stirring 1h~
2h, then sonic oscillation 30min~40min, suction filtration, are washed with distilled water at pH is about 6 or so, 90 DEG C and are vacuum dried 24h,
By the sieve of particle size selection correspondence mesh number after grinding, obtain sour attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 4:1~5:1) the acetum stirring that 100ml concentration is 1%~2%, is added, after it fully dissolves, is used
The NaOH solution regulation pH to 10 of 1mol/L, adds 20ml~30ml glutaraldehyde cross-linkings 3h~5h (60 DEG C of water-baths are stirred vigorously).
By the flocculant suction filtration after crosslinking, distillation is washed to neutrality, is obtained final product after 50 DEG C~70 DEG C vacuum drying of the present invention compound
Flocculant.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 1~5mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition 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) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, calculates the step of weighing certain volume (3) prepared by the mass ratio of chitin composite flocculant 1%~5%
CD-KH560 solution, by flocculant immerse CD-KH560 solution in, in 20 DEG C~40 DEG C shaking tables lucifuge concussion 6h~24h, institute
Freeze-drying after product distillation washing three times, obtain final product shitosan of the present invention with heavy metal ion adsorbed and detection function/
Attapulgite/carbon point composite flocculation agent.
Beneficial effect
The composite flocculation agent that the present invention solves the Adsorption of Heavy Metals ion is attapulgite modified multiple with acid using shitosan
Conjunction is prepared.Shitosan is chitin deacetylase based products, is used as flocculant, can effectively remove organic dirt in water
Dye thing, 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, the flocculant prepared with it can be while heavy metal ion in adsorbing water.Therefore, this
Composite flocculation agent prepared by mesh can play shitosan and the respective advantage of attapulgite, cooperate with its flocculation, improve compound
The scope of application and flocculation efficiency of flocculant.In addition, shitosan/attapulgite clay compounded flocculant reduces the consumption of shitosan,
Reduce cost.
Prepared by the present invention is to monitor the composite flocculation agent with heavy-metal ion removal, uses blending and surface connects
Branch method, the composite flocculation agent product can simultaneously adsorb and monitor heavy metal ion, and heavy metal ion adsorbed property is excellent, and fluorescence is quenched
Going out property is protruded.Composite flocculation agent product of the present invention fluorescence in heavy metal ion solution is presented and weakened or quenching effect, this
Planting response 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
Eliminating rate of absorption etc. heavy metal ion reaches more than 90%.Therefore, not only heavy metal ion has excellent to product of the present invention
Removal effect, moreover it is possible to there is real-time monitoring to act on the heavy metal ion in water quality.
Compared with prior art, composite flocculation agent preparation method of the present invention has process is simple, does not need special installation, work
Industryization is implemented easy.Product technology shitosan of the present invention has larger 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 is more fully understood, but limit never in any form
The present invention
Embodiment 1
(1) pretreatment of attapulgite.The attapulgite of the mesh of 10g particle diameters 300 is weighed, water washing is distilled with 1L, it is to be precipitated
After take its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, in supernatant liquor plus after a small amount of distilled water is well mixed
Continue 500rpm centrifugation 1min, then take its supernatant liquor, after such cyclic washing supernatant liquor 3 times, finally entered with 4000rpm
Row centrifugation, takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding,
Attapulgite must be purified.
Configuration concentration for 0.5mol/L hydrochloric acid solution, take 10g purifying attapulgite be added to 150mL hydrochloric acid solutions it is small
Mixing is stirred in beaker, after 5min, 70 DEG C is heated the mixture to, 1h is stirred, then sonic oscillation 30min, suction filtration, with distillation
Water washing is about at 6 or so, 90 DEG C to pH and is vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding,
Obtain sour attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 4:1) the acetum stirring that 100ml concentration is 1%, is added, after it fully dissolves, the NaOH of 1mol/L is used
Solution adjusts pH to 10, adds 20ml glutaraldehyde cross-linkings 3h (60 DEG C of water-baths are stirred vigorously).By the flocculant suction filtration after crosslinking, steam
Distilled water is washed till neutrality, and composite flocculation agent of the present invention is obtained final product after 50 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 1mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is that CD is molten
The 5% of liquid product.Uniform stirring 15h at 20 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, the CD- as prepared by the mass ratio of chitin composite flocculant 1% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 6h in 20 DEG C of shaking tables, products therefrom distillation washing three
Secondary rear freeze-drying, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function and is combined
Flocculant.
Embodiment 2
(1) pretreatment of attapulgite.The attapulgite of the mesh of 10g particle diameters 1000 is weighed, water washing is distilled with 1L, precipitation takes
Its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, is continued in supernatant liquor plus after a small amount of distilled water is well mixed
500rpm is centrifuged 1min, then takes its supernatant liquor, after such cyclic washing supernatant liquor 3 times, finally carried out with 4000rpm from
The heart is separated, and takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding, obtains pure
Change attapulgite.
Configuration concentration for 0.5mol/L hydrochloric acid solution, take 20g purifying attapulgite be added to 150mL hydrochloric acid solutions it is small
Mixing is stirred in beaker, after 5min, 70 DEG C is heated the mixture to, 1h is stirred, then sonic oscillation 30min, suction filtration, with distillation
Water washing is about at 6 or so, 90 DEG C to pH and is vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding,
Obtain sour attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 4:1) the acetum stirring that 100ml concentration is 2%, is added, after it fully dissolves, the NaOH of 1mol/L is used
Solution adjusts pH to 10, adds 20ml glutaraldehyde cross-linkings 3h (60 DEG C of water-baths are stirred vigorously).By the flocculant suction filtration after crosslinking, steam
Distilled water is washed till neutrality, and composite flocculation agent of the present invention is obtained final product after 50 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 2mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is that CD is molten
The 8% of liquid product.Uniform stirring 15h at 20 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, the CD- as prepared by the mass ratio of chitin composite flocculant 2% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 12h in 30 DEG C of shaking tables, products therefrom distillation washing three
Secondary rear freeze-drying, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function and is combined
Flocculant.
Embodiment 3
(1) pretreatment of attapulgite.The attapulgite of the mesh of 20g particle diameters 300 is weighed, water washing is distilled with 1L, precipitation takes
Its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, is continued in supernatant liquor plus after a small amount of distilled water is well mixed
500rpm is centrifuged 1min, then takes its supernatant liquor, after such cyclic washing supernatant liquor 5 times, finally carried out with 4000rpm from
The heart is separated, and takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 3mol/L, takes 10g purifying attapulgites and is added to small burning with 150mL hydrochloric acid solutions
Mixing is stirred in cup, after 5min, 80 DEG C is heated the mixture to, 2h is stirred, then sonic oscillation 30min, suction filtration, use distilled water
Wash to be about at 6 or so, 90 DEG C to pH and be vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding, obtain
Acid is attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 5:1) the acetum stirring that 100ml concentration is 2%, is added, after it fully dissolves, the NaOH of 1mol/L is used
Solution adjusts pH to 10, adds 20ml glutaraldehyde cross-linkings 5h (60 DEG C of water-baths are stirred vigorously).By the flocculant suction filtration after crosslinking, steam
Distilled water is washed till neutrality, and composite flocculation agent of the present invention is obtained final product after 70 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 5mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is that CD is molten
The 20% of liquid product.Uniform stirring 30h at 50 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, the CD- as prepared by the mass ratio of chitin composite flocculant 3% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 24h in 40 DEG C of shaking tables, products therefrom distillation washing three
Secondary rear freeze-drying, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function and is combined
Flocculant.
Embodiment 4
(1) pretreatment of attapulgite.The attapulgite of the mesh of 15g particle diameters 500 is weighed, water washing is distilled with 1L, precipitation takes
Its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, is continued in supernatant liquor plus after a small amount of distilled water is well mixed
500rpm is centrifuged 1min, then takes its supernatant liquor, after such cyclic washing supernatant liquor 5 times, finally carried out with 4000rpm from
The heart is separated, and takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 1mol/L, takes 12g purifying attapulgites and is added to small burning with 180mL hydrochloric acid solutions
Mixing is stirred in cup, after 5min, 70 DEG C is heated the mixture to, 1h is stirred, then sonic oscillation 30min, suction filtration, use distilled water
Wash to be about at 6 or so, 90 DEG C to pH and be vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding, obtain
Acid is attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 5:1) the acetum stirring that 100ml concentration is 1.5%, is added, after it fully dissolves, uses 1mol/L's
NaOH solution adjusts pH to 10, adds 30ml glutaraldehyde cross-linkings 4h (60 DEG C of water-baths are stirred vigorously).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, and composite flocculation agent of the present invention is obtained final product after 60 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 4mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is that CD is molten
The 15% of liquid product.Uniform stirring 20h at 40 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, the CD- as prepared by the mass ratio of chitin composite flocculant 4% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 30h in 35 DEG C of shaking tables, products therefrom distillation washing three
Secondary rear freeze-drying, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function and is combined
Flocculant.
Embodiment 5
(1) pretreatment of attapulgite.The attapulgite of the mesh of 16g particle diameters 800 is weighed, water washing is distilled with 1L, precipitation takes
Its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, is continued in supernatant liquor plus after a small amount of distilled water is well mixed
500rpm is centrifuged 1min, then takes its supernatant liquor, after such cyclic washing supernatant liquor 5 times, finally carried out with 4000rpm from
The heart is separated, and takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding, obtains pure
Change attapulgite.
Configuration concentration for 2.5mol/L hydrochloric acid solution, take 18g purifying attapulgite be added to 160mL hydrochloric acid solutions it is small
Mixing is stirred in beaker, after 5min, 70 DEG C is heated the mixture to, 2h is stirred, then sonic oscillation 40min, suction filtration, with distillation
Water washing is about at 6 or so, 90 DEG C to pH and is vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding,
Obtain sour attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 5:1) the acetum stirring that 100ml concentration is 1.8%, is added, after it fully dissolves, uses 1mol/L's
NaOH solution adjusts pH to 10, adds 25ml glutaraldehyde cross-linkings 5h (60 DEG C of water-baths are stirred vigorously).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, and composite flocculation agent of the present invention is obtained final product after 70 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 5mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is that CD is molten
The 20% of liquid product.Uniform stirring 24h at 40 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, the CD- as prepared by the mass ratio of chitin composite flocculant 5% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 24h in 40 DEG C of shaking tables, products therefrom distillation washing three
Secondary rear freeze-drying, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function and is combined
Flocculant.
Embodiment 6
(1) pretreatment of attapulgite.The attapulgite of the mesh of 18g particle diameters 1000 is weighed, water washing is distilled with 1L, precipitation takes
Its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, is continued in supernatant liquor plus after a small amount of distilled water is well mixed
500rpm is centrifuged 1min, then takes its supernatant liquor, after such cyclic washing supernatant liquor 5 times, finally carried out with 4000rpm from
The heart is separated, and takes its precipitation, and 24h is vacuum dried at 90 DEG C, by the sieve of particle size selection correspondence mesh number after grinding, obtains pure
Change attapulgite.
Configuration concentration is the hydrochloric acid solution of 3mol/L, takes 20g purifying attapulgites and is added to small burning with 180mL hydrochloric acid solutions
Mixing is stirred in cup, after 5min, 75 DEG C is heated the mixture to, 1.5h is stirred, then sonic oscillation 35min, suction filtration, with distillation
Water washing is about at 6 or so, 90 DEG C to pH and is vacuum dried 24h, by the sieve of particle size selection correspondence mesh number after grinding,
Obtain sour attapulgite modified.
(2) preparation of chitin composite flocculant.The 4g shitosans attapulgite modified with a certain amount of acid is weighed to mix
(mass ratio 4:1) the acetum stirring that 100ml concentration is 1.6%, is added, after it fully dissolves, uses 1mol/L's
NaOH solution adjusts pH to 10, adds 25ml glutaraldehyde cross-linkings 4h (60 DEG C of water-baths are stirred vigorously).Flocculant after crosslinking is taken out
Filter, distillation is washed to neutrality, and composite flocculation agent of the present invention is obtained final product after 60 DEG C of vacuum drying.
(3) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, is dissolved in deionized water, be made into
Solution concentration is the CD solution of 3.8mg/mL.A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is CD
The 18% of liquor capacity.Uniform stirring 30h at 36 DEG C, obtains CD-KH560 solution.
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent.Weigh prepared shitosan in 10mg steps (2)
Composite flocculation agent, as prepared by the mass ratio of chitin composite flocculant 3.8% calculates the step of weighing certain volume (3)
CD-KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 20h, products therefrom distilled water in 25 DEG C of shaking tables
Freeze-drying after washing three times, obtains final product shitosan/attapulgite/carbon point of the present invention with heavy metal ion adsorbed and detection function
Composite flocculation agent.
Claims (2)
1. a kind of with the heavy metal ion adsorbed preparation method with the composite flocculation agent of detection function, it is characterised in that including
Following steps：
(1) pretreatment of attapulgite：The attapulgite of mesh~1000 mesh of 10g~20g particle diameters 300 is weighed, is distilled with 1L and washed
Wash, it is to be precipitated after take its supernatant liquor, its supernatant liquor is taken after 500rpm centrifugations 1min, in supernatant liquor plus a small amount of distilled water is mixed
Close it is uniform after continue 500rpm centrifugation 1min, then take its supernatant liquor, after such cyclic washing supernatant liquor 3~5 times, finally
It is centrifuged with 4000rpm, takes its precipitation, 24h is vacuum dried at 90 DEG C, by particle size selection correspondence mesh number after grinding
Sieve, obtain purifying attapulgite；
Configuration concentration is the hydrochloric acid solution of 0.5mol/L~3mol/L, takes 10g~20g purifying attapulgites and 150mL~200mL
Hydrochloric acid solution stirs mixing in being added to small beaker, after 5min, heats the mixture to 70 DEG C~80 DEG C, stirs 1h~2h, so
Sonic oscillation 30min~40min, suction filtration, are washed with distilled water at pH is about 6 or so, 90 DEG C and are vacuum dried 24h afterwards, grinding
Afterwards by the sieve of particle size selection correspondence mesh number, obtain sour attapulgite modified；
(2) preparation of chitin composite flocculant：Weigh the 4g shitosans attapulgite modified with a certain amount of acid and mix (quality
Than 4:1~5:1) the acetum stirring that 100ml concentration is 1%~2%, is added, after it fully dissolves, uses 1mol/L's
NaOH solution adjusts pH to 10, adds 20ml~30ml glutaraldehyde cross-linkings 3h~5h (60 DEG C of water-baths are stirred vigorously)；After being crosslinked
Flocculant suction filtration, distillation is washed to neutrality, composite flocculation agent of the present invention obtained final product after 50 DEG C~70 DEG C vacuum drying；
(3) preparation of KH560 carbon modifieds point：The CD solids of certain mass are weighed, is dissolved in deionized water, wiring solution-forming
Concentration is the CD solution of 1~5mg/mL；A certain amount of KH560 is added in the carbon point aqueous solution, the addition of KH560 is CD solution
The 5%~20% of volume；15~30h of uniform stirring at 20 DEG C~50 DEG C, obtains CD-KH560 solution；
(4) prepared by shitosan/attapulgite/carbon point composite flocculation agent：Prepared shitosan in 10mg steps (2) is weighed to be combined
Flocculant, the CD- as prepared by the mass ratio of chitin composite flocculant 1%~5% calculates the step of weighing certain volume (3)
KH560 solution, flocculant is immersed in CD-KH560 solution, lucifuge concussion 6h~24h, products therefrom in 20 DEG C~40 DEG C shaking tables
Freeze-drying after washing three times is distilled, shitosan/concave convex rod of the present invention with heavy metal ion adsorbed and detection function is obtained final product
Soil/carbon point composite flocculation agent.
2. it is a kind of with heavy metal ion adsorbed and detection function composite flocculation agent, it is characterised in that as described in claim 1
A kind of prepared with heavy metal ion adsorbed and detection function the preparation method of composite flocculation agent.
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| CN109100339A (en) * | 2018-07-30 | 2018-12-28 | 四川大学 | A kind of kit and detection method for selective enumeration method Pb ion and Ag ion concentration |
| CN109174046A (en) * | 2018-09-30 | 2019-01-11 | 天津市金鳞水处理科技有限公司 | A kind of preparation method of detection and absorption heavy metal ion type microgel |
| CN109174047A (en) * | 2018-09-30 | 2019-01-11 | 天津市金鳞水处理科技有限公司 | One kind having both detection of heavy metal ion and absorbent-type polyacrylamide microgel |
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