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CN106622156B - A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method - Google Patents

A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method Download PDF

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CN106622156B
CN106622156B CN201611116806.2A CN201611116806A CN106622156B CN 106622156 B CN106622156 B CN 106622156B CN 201611116806 A CN201611116806 A CN 201611116806A CN 106622156 B CN106622156 B CN 106622156B
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solution
heavy metal
metal ion
attapulgite
atp
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CN106622156A (en
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赵义平
文梦娟
姜文哲
曹小浩
赵国部
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Huajian Measurement And Testing Tianjin Co ltd
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Tianjin Jinlin Water Treatment Science & Technology Co Ltd
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Priority to CN201811294087.2A priority patent/CN109289790B/en
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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"
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Abstract

The invention discloses a kind of heavy metal ion adsorbed and detection type composite hydrogel preparation methods, belong to polymeric material field.The composite hydrogel is a kind of calcium alginate/attapulgite/carbon dots composite hydrogel, is prepared by following methods: (1) using sodium alginate and attapulgite for raw material, the cross-linking formation calcium alginate hydrogel CA/ATP in ionic calcium soln；(2) modification is carried out to commercially available calcium point with coupling agent 3- glycidyloxypropyl trimethoxy silane (KH560), prepares the modified carbon dots of KH560；(3) the modified carbon dots of calcium alginate hydrogel CA/ATP and KH560 are immersed in CD-KH560 solution, by being protected from light concussion, washing, freeze-drying in shaking table, obtains heavy metal ion adsorbed and detection type composite hydrogel.The composite hydrogel not only can effectively carry out the heavy metal ion in qualitative detection, but also adsorbable water to the heavy metal ion in water.

Description

A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method
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, mercury have good The composite high-molecular hydrogel preparation method of good detection function and adsorption function.The composite hydrogel both can be effectively in water Conventional heavy metal ion carry out qualitative detection, and the heavy metal ion in water can be adsorbed, can be applied to electroplating industry, chemistry The process field of the sewage such as industry.
Background technique
Heavy metal ion pollution generates serious harm to human body.Currently, the master of harmless treatment heavy metal ion-containing waste water Method is wanted to have membrane separation process, electrochemical deposition method, ion-exchange, absorption and biological treatment etc..Wherein, absorption method is to a huge sum of money The removal rate for belonging to ion is high, and large amount of adsorption, the rate of adsorption is fast, easy to operate.But the adsorbent one of adsorbing heavy metal ions As price all costly.Therefore, with the modified existing adsorbent developing low-cost of cheap Material cladding and high absorption effect The new adsorbent of rate is an important directions of the adsorbent research of adsorbing heavy metal ions.
Attapulgite (ATP) is used as a kind of natural non-metallic mineral material, is a kind of with the aqueous of chain layer structure Rich magnesium silicate clay mineral, special structure make it have very big specific surface area, and physical absorption is very capable；Another party Face, attapulgite has level negative electrical charge, in cation of the Inter layer adsorption with interchangeability so that charge balance, recessed in this way Convex stick soil is just provided with strong ionic adsorption exchange capacity, can be applied in the wastewater treatment containing heavy metal ion.But it is recessed Convex stick soil has good suspension in water, powdered for water treatment field although it is with good adsorption capacity Attapulgite can not direct plunge into water and use, need that certain method is taken to be handled.Currently, preferable processing method It is to use certain immobilized attapulgite of carrier, then put into water and use.The present inventor discloses a kind of suction in invention early period The preparation method of attached type macromolecule composite hydrogel and products thereof (patent No. ZL201020595998.1), utilizes macromolecule water-setting Glue makees carrier, immobilized attapulgite, to play the suction-operated of attapulgite well.In addition, disclosing a kind of to a huge sum of money Belong to the preparation method of chitin composite flocculant that ionic adsorption amount is big, adsorption efficiency is high and products thereof (CN103274509A).
Sodium alginate (SA) is odorless, tasteless, faint yellow unsetting powder, function admirable, food, weaving, medicine and The various fields extensive application such as daily-use chemical industry is easy to form calcium alginate (CA) gel in ionic calcium soln, to a huge sum of money Belonging to ion has good adsorption properties.Modified be added in calcium alginate film of natural A TP is prepared for hydridization by Guerra D L etc. Laminated film has studied hybridized film to absorption property [Guerra D L, Viana R R, da Costa the L P, et of Th al.RETRACTED:Sodium alginate films modified by raw and functionalized attapulgite for use of thorium(IV)adsorption:A thermodynamic approach[J] .Journal of Physics and Chemistry of Solids,2009,70(11):1413-1421.].Li Y etc. will Carbon nanotube is fixed in calcium alginate, prepares fibrous plural gel, and result of study shows that fibrous gel can increase it Specific surface area improves absorption property [Li Y, Liu F, Xia B, the et al.Removal of copper to copper ion aqueous solution by carbon nanotube/calcium alginate composites[J].Journal of Hazardous Materials,2010,177(1):876-880.].It therefore, is carrier cladding with calcium alginate gel, fixed Attapulgite, the characteristics of its good absorption property and excellent formability can be made full use of, cooperate with the heavy metal of attapulgite from Sub- suction-operated prepares heavy metal ion adsorbed type gel rubber material.
But heavy metal ion adsorbing material generally only has single heavy metal ion adsorbed function, Bu Nengtong at present When heavy metal ion is detected.Lot of domestic and international researcher is dedicated to heavy metal ion Pollution Study, designs one kind Not only had good absorption property but 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
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve, which is to provide one kind, can adsorb and monitor simultaneously weight The preparation method of the macromolecule hydrogel of metal ion.The composite hydrogel is that a kind of calcium alginate/attapulgite/carbon dots are compound Hydrogel not only effectively can carry out qualitative detection to the conventional heavy metal ion in water, but also can adsorb the heavy metal in water Ion.
Product of the present invention uses sodium alginate and attapulgite for raw material, the cross-linking formation sea in ionic calcium soln Calcium alginate hydrogel CA/ATP.Product of the present invention uses commercially available carbon dots, with coupling agent 3- glycidyloxypropyl three Methoxy silane (KH560) is modified processing to it, prepares the modified carbon dots of KH560.
Of the present invention heavy metal ion adsorbed and detection type composite hydrogel is made by following methods:
(1) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 1% ~5% SA solution.The ATP of SA content 10%~50% is added into SA solution, stirs so that ATP sufficiently divides in the solution It dissipates, obtains gel feed liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, quickly immersing 20 DEG C~50 DEG C concentration is 1% ~5% CaCl2In solution, crosslinking solidification 10h~15h molding obtains CA/ATP aquagel membrane.Product is constantly washed with distilled water It washs, to remove the Ca of surface2+.It is freeze-dried after washing gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel film 1%~5% weighs certain volume (2), will coagulate Glue film immerses in CD-KH560 solution, concussion 6h~for 24 hours is protected from light in 20 DEG C~40 DEG C shaking tables, after products therefrom distillation washing three times Freeze-drying is to get a kind of heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel of the invention.
Beneficial effect
It is the plural gel of monitoring and heavy-metal ion removal prepared by the present invention, using blending and surface grafting Method, which can adsorb and monitor simultaneously heavy metal ion, and heavy metal ion adsorbed property is excellent, fluorescent quenching It is prominent, it is a kind of novel alga acid calcium composite hydrogel product.Plural gel product of the present invention is in heavy metal ion solution Decrease or quenching effect, such responsiveness is presented in middle fluorescence can reach real-time monitoring purpose to water quality.It is of the present invention compound solidifying Glue product reaches 90% or more to the eliminating rate of absorption of the heavy metal ion such as low concentration nickel, chromium, lead, mercury.Therefore, the present invention produces Product not only have excellent removal to act on heavy metal ion, moreover it is possible to have real-time monitoring effect to the heavy metal ion in water quality.
Compared with prior art, plural gel preparation method of the present invention has simple process, does not need special installation, industry Change and implements to be easy.Product of the present invention technology CA has biggish covering amount to ATP, so that product cost is low, and storeroom is compatible Property is good.
Attapulgite of the present invention is as a kind of natural non-metallic inorganic mineral material, and cheap, storage is abundant. Carbon dots of the present invention are common commercially available carbon dots.Using the technology of the present invention, ATP can be easy to surface grafting CD.
After plural gel absorption heavy metal ion of the present invention, a huge sum of money for high efficiente callback absorption can be cleaned by cleaning solution Belong to ion, can disposably wash away 95% or more adsorbed heavy metal ion, gel may be reused.
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) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 1% SA solution.The ATP of SA content 10% is added into SA solution, stirring obtains gel material so that ATP is fully dispersed in the solution Liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, the CaCl that 20 DEG C of concentration are 1% is quickly immersed2In solution, crosslinking 10h molding is solidified, CA/ATP aquagel membrane is obtained.Product is constantly washed with distilled water, to remove the Ca of surface2+.Washing It is freeze-dried after gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel 1% weighs certain volume (2), gel is immersed In CD-KH560 solution, concussion 6h is protected from light in 20 DEG C of shaking tables, products therefrom distillation washing is freeze-dried afterwards to get the present invention three times A kind of heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel.
Embodiment 2
(1) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 2% SA solution.The ATP of SA content 20% is added into SA solution, stirring obtains gel material so that ATP is fully dispersed in the solution Liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, the CaCl that 30 DEG C of concentration are 2% is quickly immersed2In solution, crosslinking 10h molding is solidified, CA/ATP aquagel membrane is obtained.Product is constantly washed with distilled water, to remove the Ca of surface2+.Washing It is freeze-dried after gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel 2% weighs certain volume (2), gel is immersed In CD-KH560 solution, concussion 10h is protected from light in 20 DEG C of shaking tables, products therefrom distillation washing is freeze-dried afterwards to get this hair three times Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel.
Embodiment 3
(1) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 3% SA solution.The ATP of SA content 30% is added into SA solution, stirring obtains gel material so that ATP is fully dispersed in the solution Liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, the CaCl that 40 DEG C of concentration are 3% is quickly immersed2In solution, crosslinking 15h molding is solidified, CA/ATP aquagel membrane is obtained.Product is constantly washed with distilled water, to remove the Ca of surface2+.Washing It is freeze-dried after gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel 3% weighs certain volume (2), gel is immersed In CD-KH560 solution, concussion is protected from light in 40 DEG C of shaking tables for 24 hours, products therefrom distillation washing is freeze-dried afterwards to get this hair three times Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel.
Embodiment 4
(1) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 3% SA solution.The ATP of SA content 40% is added into SA solution, stirring obtains gel material so that ATP is fully dispersed in the solution Liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, the CaCl that 35 DEG C of concentration are 4% is quickly immersed2In solution, crosslinking 12h molding is solidified, CA/ATP aquagel membrane is obtained.Product is constantly washed with distilled water, to remove the Ca of surface2+.Washing It is freeze-dried after gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel 3% weighs certain volume (2), gel is immersed In CD-KH560 solution, concussion 12h is protected from light in 30 DEG C of shaking tables, products therefrom distillation washing is freeze-dried afterwards to get this hair three times Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel.
Embodiment 5
(1) preparation of CA/ATP plural gel.A certain amount of SA is dissolved in 100g deionized water, being made into concentration is 5% SA solution.The ATP of SA content 50% is added into SA solution, stirring obtains gel material so that ATP is fully dispersed in the solution Liquid.Feed liquid is inclined into glass plate, is formed a film with glass bar striking, the CaCl that 50 DEG C of concentration are 5% is quickly immersed2In solution, crosslinking 15h molding is solidified, CA/ATP aquagel membrane is obtained.Product is constantly washed with distilled water, to remove the Ca of surface2+.Washing It is freeze-dried after gained hydrogel product, it is spare.
(2) 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.
(3) prepared by CA/ATP/CD plural gel.Prepared CA/ATP gel mould in 10mg step (1) is weighed, by CA/ATP CD-KH560 solution prepared by the step of mass ratio calculating of plural gel 5% weighs certain volume (2), gel is immersed In CD-KH560 solution, concussion 18h is protected from light in 30 DEG C of shaking tables, products therefrom distillation washing is freeze-dried afterwards to get this hair three times Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite hydrogel.

Claims (1)

1. a kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method, which comprises the following steps:
(1) calcium alginate/attapulgite clay compounded gel preparation: a certain amount of sodium alginate is dissolved in 100g deionized water, It is made into the sodium alginate soln that concentration is 1%~5%；Sodium alginate content 10%~50% is added into sodium alginate soln Attapulgite, stirring obtain gel feed liquid so that attapulgite is fully dispersed in the solution；Feed liquid is inclined into glass plate, uses glass Glass stick striking film forming quickly immerses the CaCl that 20 DEG C~50 DEG C concentration are 1%~5%2In solution, crosslinking solidification 10h~15h at Type obtains calcium alginate/attapulgite aquagel membrane；Product is constantly washed with distilled water, to remove the Ca of surface2+；It washes It is freeze-dried after washing gained hydrogel product, it is spare；
(2) preparation of the modified carbon dots of 3- glycidyloxypropyl trimethoxy silane: the carbon quantum dot of certain mass is weighed Solid is dissolved in deionized water, and wiring solution-forming concentration is the carbon quantum dot solution of 1~5mg/mL；It adds a certain amount of 3- glycidyloxypropyl trimethoxy silane is in carbon dots aqueous solution, 3- glycidyloxypropyl trimethoxy silicon The additive amount of alkane is the 5%~20% of carbon quantum dot liquor capacity；15~30h of uniform stirring at 20 DEG C~50 DEG C, obtains carbon amounts Sub- point -3- glycidyloxypropyl trimethoxy silane solution；
(3) calcium alginate/attapulgite/carbon quantum dot plural gel preparation: prepared alginic acid in 10mg step (1) is weighed Calcium/attapulgite gel mould weighs certain body by the calculating of calcium alginate/attapulgite clay compounded gel mould 1%~5% mass ratio Carbon quantum dot -3- glycidyloxypropyl trimethoxy silane solution, gel mould is immersed prepared by long-pending step (2) In carbon quantum dot -3- glycidyloxypropyl trimethoxy silane solution, be protected from light in 20 DEG C~40 DEG C shaking tables concussion 6h~ For 24 hours, products therefrom distillation washing is freeze-dried afterwards three times to get a kind of heavy metal ion adsorbed and detection type alginic acid of the invention Calcium/attapulgite/carbon quantum dot composite hydrogel.
CN201611116806.2A 2016-12-07 2016-12-07 A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method Active CN106622156B (en)

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