CN106622156A - Preparation method of composite hydrogel for adsorbing and detecting heavy metal ions - Google Patents

Preparation method of composite hydrogel for adsorbing and detecting heavy metal ions Download PDF

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CN106622156A
CN106622156A CN201611116806.2A CN201611116806A CN106622156A CN 106622156 A CN106622156 A CN 106622156A CN 201611116806 A CN201611116806 A CN 201611116806A CN 106622156 A CN106622156 A CN 106622156A
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solution
atp
heavy metal
preparation
gel
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CN106622156B (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 CN201811293892.3A priority patent/CN109289789B/en
Priority to CN201811294087.2A priority patent/CN109289790B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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"
    • G01N2021/6432—Quenching

Abstract

The invention discloses a preparation method of a composite hydrogel for adsorbing and detecting heavy metal ions, and belongs to the field of high polymer materials. The composite hydrogel is a calcium alginate/attapulgite/carbon-point composite hydrogel and is prepared by the following steps of (1) adopting calcium alginate and attapulgite as raw materials and forming a calcium alginate hydrogel CA/ATP in a calcium ion solution by means of crosslinking; (2) carrying out modifying treatment on commercially available calcium points by using a coupling agent 3-glycoxyl trimethoxysilane (KH560) to prepare KH560 modified carbon points; (3) immersing calcium alginate hydrogel CA/ATP and the KH560 modified carbon points into a CD-KH560 solution, carrying out light-proof oscillation, washing and freeze-drying in a table concentrator to prepare the composite hydrogel for adsorbing and detecting the heavy metal ions. According to the composite hydrogel, qualitative detection can be effectively carried out on the heavy metal ions in water and the heavy metal ions in the water can be adsorbed.

Description

A kind of preparation method of heavy metal ion adsorbed and detection type composite aquogel
Technical field
The present invention relates to polymeric material field, and in particular to it is a kind of the heavy metal ion such as nickel, chromium, lead, mercury are had it is good The composite high-molecular hydrogel preparation method of function and adsorption function is detected well.The composite aquogel both can effectively in water Conventional heavy metal ion carry out qualitative detection, the heavy metal ion in water can be adsorbed again, can be applicable to electroplating industry, chemistry The process field of the sewage such as industry.
Background technology
Heavy metal ion pollution produces serious harm to human body.At present, 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 clearance of category ion is high, and adsorbance is big, and the rate of adsorption is fast, easy to operate.But, the adsorbent one of adsorbing heavy metal ions As price all costly.Therefore, it is modified existing adsorbent developing low-cost and high absorption effect with cheap Material cladding The new adsorbent of rate, is an important directions of the adsorbent research of adsorbing heavy metal ions.
Attapulgite (ATP), 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, its special structure makes it have very big specific surface area, and physical absorption is very capable；The opposing party Face, attapulgite carries aspect negative electrical charge, and in Inter layer adsorption, the cation with interchangeability is so that charge balance, so recessed Convex rod soil is just provided with strong ionic adsorption exchange capacity, in may apply to the wastewater treatment containing heavy metal ion.But, it is recessed Convex rod soil has good suspension in water, although it has good adsorption capacity, for water treatment field, powder Attapulgite cannot direct plunge into used in water, need to take certain method to be processed.At present, preferable processing method It is to adopt certain immobilized attapulgite of carrier, then puts into used in water.The present inventor discloses a kind of suction in early stage invention The preparation method of attached type macromolecule composite aquogel and products thereof (patent No. ZL201020595998.1), using macromolecule water-setting Glue makees carrier, immobilized attapulgite, so as to play the suction-operated of attapulgite well.In addition, disclosing a kind of to a huge sum of money The category 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, it is easy to calcium alginate (CA) gel is formed in ionic calcium soln, to a huge sum of money Category ion has good adsorption properties.Modified being added in calcium alginate film of natural A TP is prepared for hydridization by Guerra D L etc. Laminated film, have studied absorption property of the hybridized film to Th【Guerra D L,Viana R R,da Costa L P,et 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 CNT is fixed in calcium alginate, prepares fibrous plural gel, and result of study shows, fibrous gel can increase it Specific surface area, improves the absorption property to copper ion【Li Y,Liu F,Xia B,et al.Removal of copper from aqueous solution by carbon nanotube/calcium alginate composites[J].Journal of Hazardous Materials,2010,177(1):876-880.】.Therefore, it is carrier cladding, fixed with calcium alginate gel 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, current heavy metal ion adsorbing material typically only has single heavy metal ion adsorbed function, it is impossible to same When heavy metal ion detected.Lot of domestic and international researcher is devoted to heavy metal ion Pollution Study, and design is a kind of Not only had good absorption property but 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 little, cheap, with very peculiar chemistry and Physical property and possess strong fluorescence, water-soluble and biocompatibility etc., can be applicable to bio-imaging, medical diagnosis, urge In agent, photovoltaic device, while the characteristic for being easy to be quenched by metal ion causes in recent years the very big concern of researchers, 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, explore in water treatment field and have simultaneously Standby to adsorb and detect that the material of heavy metal ion is also few, i.e., absorption and tluorimetric composite have very big using front Scape.
The content of the invention
For the deficiencies in the prior art, the technical problem that the present invention is intended to solve is to provide one kind can be while adsorb and monitor weight The preparation method of the macromolecule hydrogel of metal ion.The composite aquogel is compound for a kind of calcium alginate/attapulgite/carbon point Hydrogel, both can effectively to water in conventional heavy metal ion carry out qualitative detection, the heavy metal in water can be adsorbed again Ion.
Product of the present invention adopts sodium alginate and attapulgite for raw material, cross-linking in ionic calcium soln to form sea Calcium alginate hydrogel CA/ATP.Product of the present invention adopts commercially available carbon point, with coupling agent 3- glycidyloxypropyls three Methoxy silane (KH560) is modified process to it, prepares KH560 carbon modifieds point.
Of the present invention heavy metal ion adsorbed and detection type composite aquogel is obtained by following methods：
(1) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 1% ～5% SA solution.Add the ATP of SA contents 10%～50%, stirring that ATP is fully divided in the solution in SA solution Dissipate, obtain gel feed liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 20 DEG C～50 DEG C concentration of immersion are 1% ～5% CaCl2In solution, crosslinking solidification 10h～15h shapings obtain CA/ATP aquagel membranes.Product distilled water is constantly washed Wash, to remove the Ca of its surface2+.Freeze-drying is carried out after washing gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 1～5mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel film 1%～5% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), will be solidifying In glued membrane immersion CD-KH560 solution, lucifuge concussion 6h～24h in 20 DEG C～40 DEG C shaking tables, after products therefrom distillation washes three times Freeze-drying, obtains final product a kind of heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel of the invention.
Beneficial effect
Prepared by the present invention is the plural gel of monitoring and heavy-metal ion removal, uses blending and surface grafting Method, the plural gel product can simultaneously adsorb and monitor 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 aquogel product.Plural gel product of the present invention is in heavy metal ion solution Middle fluorescence is presented and weakened or quenching effect, and this kind of response can reach real-time monitoring purpose to water quality.It is of the present invention compound solidifying Glue product reaches more than 90% to the eliminating rate of absorption of the heavy metal ion such as low concentration nickel, chromium, lead, mercury.Therefore, the present invention is produced Not only heavy metal ion has excellent removal effect to product, moreover it is possible to have real-time monitoring to act on the heavy metal ion in water quality.
Compared with prior art, plural gel preparation method of the present invention has process is simple, does not need special installation, industry Change and implement easy.Product technology CA of the present invention has larger covering amount to ATP, and so as to product cost is low, and storeroom is compatible Property is good.
Attapulgite of the present invention is cheap as a kind of natural non-metallic inorganic mineral material, and storage is abundant. Carbon point of the present invention is common commercially available carbon point.Using the technology of the present invention, ATP can be easy to surface grafting CD.
After plural gel Adsorption of Heavy Metal Ions of the present invention, a huge sum of money for high efficiente callback absorption can be cleaned by cleaning fluid Category ion, can disposably wash away more than 95% heavy metal ion adsorbed, and gel can be reused.
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) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 1% SA solution.The ATP of SA contents 10%, stirring is added to cause ATP fully dispersed in the solution, obtain gel material in SA solution Liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 20 DEG C of concentration of immersion are 1% CaCl2In solution, crosslinking Solidification 10h shapings, obtain CA/ATP aquagel membranes.Product distilled water is constantly washed, to remove the Ca of its surface2+.Washing Freeze-drying is carried out after gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 1mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel 1% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), and gel is immersed In CD-KH560 solution, lucifuge concussion 6h in 20 DEG C of shaking tables, products therefrom distills freeze-drying after washing three times, obtains final product the present invention A kind of heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel.
Embodiment 2
(1) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 2% SA solution.The ATP of SA contents 20%, stirring is added to cause ATP fully dispersed in the solution, obtain gel material in SA solution Liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 30 DEG C of concentration of immersion are 2% CaCl2In solution, crosslinking Solidification 10h shapings, obtain CA/ATP aquagel membranes.Product distilled water is constantly washed, to remove the Ca of its surface2+.Washing Freeze-drying is carried out after gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 2mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel 2% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), and gel is immersed In CD-KH560 solution, lucifuge concussion 10h in 20 DEG C of shaking tables, products therefrom distills freeze-drying after washing three times, obtains final product this Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel.
Embodiment 3
(1) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 3% SA solution.The ATP of SA contents 30%, stirring is added to cause ATP fully dispersed in the solution, obtain gel material in SA solution Liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 40 DEG C of concentration of immersion are 3% CaCl2In solution, crosslinking Solidification 15h shapings, obtain CA/ATP aquagel membranes.Product distilled water is constantly washed, to remove the Ca of its surface2+.Washing Freeze-drying is carried out after gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 5mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel 3% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), and gel is immersed In CD-KH560 solution, lucifuge concussion 24h in 40 DEG C of shaking tables, products therefrom distills freeze-drying after washing three times, obtains final product this Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel.
Embodiment 4
(1) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 3% SA solution.The ATP of SA contents 40%, stirring is added to cause ATP fully dispersed in the solution, obtain gel material in SA solution Liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 35 DEG C of concentration of immersion are 4% CaCl2In solution, crosslinking Solidification 12h shapings, obtain CA/ATP aquagel membranes.Product distilled water is constantly washed, to remove the Ca of its surface2+.Washing Freeze-drying is carried out after gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 4mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel 3% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), and gel is immersed In CD-KH560 solution, lucifuge concussion 12h in 30 DEG C of shaking tables, products therefrom distills freeze-drying after washing three times, obtains final product this Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel.
Embodiment 5
(1) preparation of CA/ATP plural gels.A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 5% SA solution.The ATP of SA contents 50%, stirring is added to cause ATP fully dispersed in the solution, obtain gel material in SA solution Liquid.Feed liquid is inclined to into glass plate, with glass bar striking film forming, quick 50 DEG C of concentration of immersion are 5% CaCl2In solution, crosslinking Solidification 15h shapings, obtain CA/ATP aquagel membranes.Product distilled water is constantly washed, to remove the Ca of its surface2+.Washing Freeze-drying is carried out after gained hydrogel product, it is standby.
(2) preparation of KH560 carbon modifieds point.The CD solids of certain mass are weighed, in being dissolved in deionized water, is made into Solution concentration is the CD solution of 5mg/mL.Add a certain amount of KH560 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.
(3) prepared by CA/ATP/CD plural gels.Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, by CA/ATP The mass ratio of plural gel 5% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), and gel is immersed In CD-KH560 solution, lucifuge concussion 18h in 30 DEG C of shaking tables, products therefrom distills freeze-drying after washing three times, obtains final product this Bright one kind is heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel.

Claims (1)

1. a kind of preparation method of heavy metal ion adsorbed and detection type composite aquogel, it is characterised in that comprise the following steps：
(1) preparation of CA/ATP plural gels：A certain amount of SA is dissolved in 100g deionized waters, concentration is made into for 1%～5% SA solution；The ATP of SA contents 10%～50%, stirring is added to cause ATP fully dispersed in the solution, obtain in SA solution Gel feed liquid；Feed liquid is inclined to into glass plate, with glass bar striking film forming, quickly 20 DEG C～50 DEG C concentration of immersion are 1%～5% CaCl2In solution, crosslinking solidification 10h～15h shapings obtain CA/ATP aquagel membranes；Product distilled water is constantly washed, to remove Remove the Ca of its surface2+；Freeze-drying is carried out after washing gained hydrogel product, it is standby；
(2) preparation of KH560 carbon modifieds point：Weigh the CD solids of certain mass, in being dissolved in deionized water, wiring solution-forming Concentration is the CD solution of 1～5mg/mL；Add a certain amount of KH560 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；
(3) prepared by CA/ATP/CD plural gels：Prepared CA/ATP gel moulds in 10mg steps (1) are weighed, it is compound by CA/ATP The mass ratio of gel mould 1%～5% calculates the CD-KH560 solution prepared by the step of weighing certain volume (2), by gel mould In immersion CD-KH560 solution, lucifuge concussion 6h～24h in 20 DEG C～40 DEG C shaking tables, products therefrom distillation is freezed after washing three times It is dried, obtains final product a kind of heavy metal ion adsorbed and detection type CA/ATP/CD composite aquogel of the invention.
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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Application Number Priority Date Filing Date Title
CN201611116806.2A CN106622156B (en) 2016-12-07 2016-12-07 A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method
CN201811293857.1A CN109289788B (en) 2016-12-07 2016-12-07 Heavy metal ion adsorption and detection type composite hydrogel
CN201811293892.3A CN109289789B (en) 2016-12-07 2016-12-07 Preparation method of composite hydrogel for heavy metal ion adsorption and detection
CN201811294087.2A CN109289790B (en) 2016-12-07 2016-12-07 Preparation method of multifunctional composite hydrogel

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CN201611116806.2A CN106622156B (en) 2016-12-07 2016-12-07 A kind of heavy metal ion adsorbed and detection type composite hydrogel preparation method

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CN201811293857.1A Division CN109289788B (en) 2016-12-07 2016-12-07 Heavy metal ion adsorption and detection type composite hydrogel
CN201811294087.2A Division CN109289790B (en) 2016-12-07 2016-12-07 Preparation method of multifunctional composite hydrogel
CN201811293892.3A Division CN109289789B (en) 2016-12-07 2016-12-07 Preparation method of composite hydrogel for heavy metal ion adsorption and detection

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