CN105148851B - A kind of Preparation method and use of urea groups functionalization cadmium ion surface imprint adsorbent - Google Patents
A kind of Preparation method and use of urea groups functionalization cadmium ion surface imprint adsorbent Download PDFInfo
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- CN105148851B CN105148851B CN201510626306.2A CN201510626306A CN105148851B CN 105148851 B CN105148851 B CN 105148851B CN 201510626306 A CN201510626306 A CN 201510626306A CN 105148851 B CN105148851 B CN 105148851B
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Abstract
The present invention relates to a kind of Preparation method and uses of urea groups functionalization cadmium ion surface imprint adsorbent, and in embodiment, preparation method includes：The inorganic cadmium salts of 1~5g and organic solvent are added in three-necked flask, 20 DEG C~80 DEG C stirring in water bath 20min~60min；Coupling agent is added, stirring obtains pre-assembled body；Then 2~15g silica gel is added, stirs 12h~48h；Crosslinking agent and initiator is added, stirs 2h~12h；Ethanol solution and second distillation water washing are used respectively；The acid solution of a concentration of 2mol/L~8mol/L is added, 2h~8h is vibrated in 25 DEG C~45 DEG C, vacuum filtration obtains sediment；Then it is 6~7 to be washed repeatedly with redistilled water to filtrate pH；Sediment after washing is positioned in vacuum drying chamber, the dry 2h~for 24 hours under the conditions of 50 DEG C~70 DEG C obtains adsorbent；The mass ratio of inorganic cadmium salt and coupling agent is 1:2.Preparation process is simple, and condition is easy to control.The adsorbent can be used for Selective Separation cadmium and/or degradation Cadmium Pollutants On The Chinese, speed are fast.
Description
Technical field
The present invention relates to environment functional material field more particularly to a kind of urea groups functionalization cadmium ion surface imprint adsorbents
Preparation method and use.
Background technology
By the extensive concern in the world, the improvement of heavy metal pollution is also global problem for heavy metal pollution.2011
Just,《Heavy metal pollution integrated control " 12th Five-Year Plan " is planned》By the audit and reply of State Council, by the prevention of heavy metal pollution
It is included in for the first time in the planning of country.
Cadmium occupies one of five big hypertoxic heavy metals, and in kidney, it not only may be used major storage savings after it is absorbed by the body
Cause renal function to fail to make the urinary system of people that lesion occur, the calcium in bone can also be replaced and put aside in skeleton
In serious softening bone so that it is easily snapped off and with the bone pain symptom of whole body.
Absorption method processing heavy metal Cd (II) effect is good, easy to operate, and imprinted polymer is pre- as adsorbent Yin Qigao's
Determine identity and selectivity is widely studied.The synthesis of ion imprinted polymer is using zwitterion as template, by quiet
The effects that electricity, coordination, is combined with function monomer, and is remained the foreseeability of molecularly imprinted polymer, specific recognition and extensive fitted
With property the advantages that.In ion imprinted polymer reserve imprinted cavity can position can be filtered out from complex matrices template from
The matching degree of son, the spatial form of the imprinted cavity left in advance and the stereoeffect of template ion is imprinted polymer pair
The key of template ion selection.
There are many disadvantages, such as template, monomer, crosslinking agent hairs for the ion imprinted polymer prepared with traditional method
Many templates can be wrapped in internal and cannot be removed after raw polymerization, and hole rate is relatively low, and maximal absorptive capacity is reduced, in conjunction with
Performance is not high.Surface ion engram technology develops comparatively fast in recent years, and this method can not only overcome these disadvantages, but also inhale
Diffusional resistance during attached reduces, and mass transfer velocity is accelerated, and hole is located at the surface of polymer, is conducive to the progress of absorption.
Invention content
That in response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of thermal stability is good, has a wide range of application, inhales
The preparation method of high, high selectivity the adsorbent of attached capacity, this method preparation process is simple, condition of low cost and synthesis is easy
In control, the application of the adsorbent is provided accordingly.
To achieve the above object, the present invention provides a kind of urea groups functionalization cadmium ion surface imprint adsorbents for first aspect
Preparation method, which includes the following steps：
The inorganic cadmium salts of 1~5g and organic solvent are added in three-necked flask, 20 DEG C~80 DEG C stirring in water bath handle 20min
~60min；
Coupling agent is added, stir process obtains pre-assembled body；
2~15g silica gel is added in the pre-assembled body, stir process 12h~48h；
Crosslinking agent and initiator, stir process 2h~12h is added；
Ethanol solution and second distillation water washing are used respectively；
The acid solution of a concentration of 2mol/L~8mol/L is added, oscillation treatment 2h~8h under the conditions of 25 DEG C~45 DEG C, very
Sky filters and obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 2h~for 24 hours is dried under the conditions of 50 DEG C~70 DEG C,
Obtain urea groups functionalization cadmium ion surface imprint adsorbent.
Preferably, the silica gel is the silica gel handled by acid activation, specially：
The acid solution of 100~200 1~50g of mesh silica gel and a concentration of 2mol/L~8mol/L of 6mL~300mL is added to
In three-necked flask；
The three-necked flask is placed in thermostat water bath, stir process 6h~12h under the conditions of 50 DEG C~100 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber drying process 8h~48h under the conditions of 50 DEG C~100 DEG C, is obtained
To the silica gel of acid activation；
Wherein, the mass ratio of inorganic cadmium salt and coupling agent is 1:2.
Preferably, the inorganic cadmium salt is caddy, cadmium nitrate or cadmium sulfate.
Preferably, the coupling agent is in γ-ureido-propyl trimethoxy silane and γ-ureidopropyltriethoxysilane
It is one or more.
Preferably, the organic solvent is methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, uncle
It is one or more in butanol, isobutanol, n-amyl alcohol, sec-amyl alcohol, tertriary amylo alcohol, isoamyl alcohol, n-hexyl alcohol and cyclohexanol.
Preferably, the crosslinking agent is ethylene glycol dimethacrylate, epoxychloropropane, N, N- methylene bisacrylamide acyls
It is one or more and described in amine, 4- urocanic acids ethyl ester, methylene-succinic acid, divinylbenzene and diisocyanate
The amount of crosslinking agent accounts for the 3%~15% of gross mass.
Preferably, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, over cure
It is one or more in sour ammonium and potassium peroxydisulfate；And the amount of the initiator accounts for the 0.1%~2% of gross mass.
Preferably, the acid solution is one kind in hydrochloric acid solution, salpeter solution, sulfuric acid solution and phosphoric acid.
Realize above-mentioned purpose, the present invention provides a kind of purposes of adsorbent as described in relation to the first aspect, institutes for second aspect
Adsorbent is stated for Selective Separation cadmium and/or degradation Cadmium Pollutants On The Chinese.
Preferably, the adsorbent includes the following steps for Selective Separation cadmium and/or degradation Cadmium Pollutants On The Chinese：
Pollution of chromium solution is added in conical flask with cover, adjusts solution ph to 2~8；
The adsorbent is added in the conical flask with cover；
Then the conical flask with cover is positioned in thermostat water bath, carries out oscillation treatment；
Wherein, the time of the oscillation treatment is 1min~30min, and bath temperature is 20 DEG C~40 DEG C.
It is an advantage of the invention that：
Acid activation silica gel makes Silica Surface have enough hydroxyl-OH, is conducive to carry out graft reaction in Silica Surface, even
Connection agent is grafted on Silica Surface and forms compound silica gel material, and the urea groups functional group of composite material surface can be to the huge sum of money such as cadmium ion
Belong to ion and generate strong chelation, is conducive to the absorption for being dissolved in middle cadmium ion.The cadmium ion prepared using surface imprinted technology
Surface imprinted adsorbent imprinted cavity is distributed in surface, and template is distributed in supporting body surface and is easy to elute to obtain larger hole
Gap rate exposes more recognition sites, is easy to the combination and elution of template ion, and the adsorber particles size of preparation can be controlled
System, and there is good thermal stability.The cadmium ion surface imprint adsorbent of preparation has specific recognition ability to cadmium ion, selection
Property is higher.And preparation process is simpler, the condition of synthesis is easy to control.The cadmium ion surface imprint adsorbent prepared with this method can
To remove the insulator in solution well, removal speed is fast, and adsorption equilibrium, and minimizing technology can be reached in 10min
Simply, easily operated.
Description of the drawings
Fig. 1 is a kind of stream of urea groups functionalization cadmium ion surface imprint sorbent preparation method provided in an embodiment of the present invention
Journey schematic diagram；
Fig. 2 is the flow diagram of silica gel acidification provided in an embodiment of the present invention；
Fig. 3 is influence of the pH value of the embodiment of the present invention to divalent cadmium ion in adsorbent solution；
Fig. 4 is influence of the initial concentration of the embodiment of the present invention to cadmium sorption
Fig. 5 is the influence of adsorption time of the embodiment of the present invention and temperature to divalent cadmium ion in adsorbent solution；
Fig. 6 is the comparison of trace of embodiment of the present invention adsorbent and non-trace adsorbent adsorption effect.
Specific implementation mode
Below by drawings and examples, technical scheme of the present invention is described in further detail, but is not intended to
It limits the scope of the invention.
An embodiment of the present invention provides a kind of preparation method of urea groups functionalization cadmium ion surface imprint adsorbent, attached drawings 1
For a kind of flow diagram of urea groups functionalization cadmium ion surface imprint sorbent preparation method provided in an embodiment of the present invention, by
Shown in Fig. 1, this approach includes the following steps：
Step 10, the inorganic cadmium salts of 1~5g and organic solvent are added in three-necked flask, at 20 DEG C~80 DEG C stirring in water bath
Manage 20min~60min；
Specifically, inorganic cadmium salt is caddy, cadmium nitrate or cadmium sulfate；Organic solvent is methanol, ethyl alcohol, ethylene glycol, just
Propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol, n-amyl alcohol, sec-amyl alcohol, tertriary amylo alcohol, isoamyl alcohol, n-hexyl alcohol and
It is one or more in cyclohexanol.
Step 20,2~10g coupling agents are added, stir process obtains pre-assembled body；
Specifically, coupling agent is one in γ-ureido-propyl trimethoxy silane and γ-ureidopropyltriethoxysilane
Kind is a variety of, and the mass ratio of inorganic cadmium salt and coupling agent is 1:2.
Step 30,2~15g silica gel is added in the pre-assembled body, 12~48h of stir process；
Specifically, silica gel is the silica gel handled by acid activation, and as shown in Figure 2, the acid activation processing procedure of silica gel is specific
For：
Step 301, the acid of 100~200 1~50g of mesh silica gel and a concentration of 2mol/L~8mol/L of 6mL~300mL is molten
Liquid is added in three-necked flask；
Step 302, the three-necked flask is placed in thermostat water bath, the stir process 6h under the conditions of 50 DEG C~100 DEG C
~12h；
Step 303, vacuum filtration obtains sediment；
Step 304, it is 6~7 the sediment to be washed repeatedly with redistilled water to filtrate pH；
Step 305, the sediment after washing is put into vacuum drying chamber, is dried under the conditions of 50 DEG C~100 DEG C
8h~48h obtains the silica gel of acid activation.
Specifically, acid solution is one kind in hydrochloric acid solution, salpeter solution, sulfuric acid solution and phosphoric acid.
Step 40, crosslinking agent and initiator, stir process 2h~12h is added；
Specifically, crosslinking agent be ethylene glycol dimethacrylate, epoxychloropropane, N, N- methylene-bisacrylamides,
It is one or more in 4- urocanic acids ethyl ester, methylene-succinic acid, divinylbenzene and diisocyanate；And the crosslinking
The amount of agent accounts for the 3%~15% of gross mass.
Initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, ammonium persulfate and persulfuric acid
It is one or more in potassium；And the amount of the initiator accounts for the 0.1%~2% of gross mass.
Step 50, ethanol solution and second distillation water washing are used respectively；
Step 60, the acid solution of a concentration of 2mol/L~8mol/L is added, in 25 DEG C~45 DEG C 2~8h of oscillation treatment, very
Sky filters and obtains sediment；
Specifically, acid solution is one kind in hydrochloric acid solution, salpeter solution, sulfuric acid solution and phosphoric acid.
Step 70, it is 6~7 the sediment to be washed repeatedly with redistilled water to filtrate pH；
Step 80, the sediment after washing is positioned in vacuum drying chamber, is dried under the conditions of 50 DEG C~70 DEG C
2h~for 24 hours, obtain urea groups functionalization cadmium ion surface imprint adsorbent.
The present embodiment carries out acid activation to silica gel first, i.e., is connect in Silica Surface during preparing adsorbent
Imprinted layer on branch reaction trace carries out acid activation to silica gel and Silica Surface is made to have enough more hydroxyl-OH, anti-for grafting condensation
Enough grafting sites should be provided, be conducive to carry out graft reaction in Silica Surface, coupling agent is grafted on Silica Surface and is formed again
There are two functional groups of different nature for the coupling agent tool for closing silica gel material, and being used in the embodiment of the present invention, can improve inorganic
Interface interaction between object and organic matter improves the performance of composite material, while can also play the role of function monomer.It is compound
The urea groups functional group on silica gel material surface can generate the heavy metal ion such as cadmium ion strong chelation, be conducive in being dissolved in
The absorption of cadmium ion.Polymerisation is carried out using polar solvent when preparing adsorbent, function base in function monomer can be excluded
Gravitation between group and solvent.The cadmium ion surface imprint adsorbent imprinted cavity prepared using surface imprinted technology is distributed in table
Face, template are distributed in supporting body surface and are easy to elute to obtain larger porosity, expose more recognition sites, be easy to
The combination and elution of template ion, and there is good thermal stability, in addition, because the size and crosslinking agent of adsorber particles
Concentration is related, so the adsorber particles size prepared can control.The cadmium ion surface imprint adsorbent of preparation is to cadmium ion
There are specific recognition ability, selectivity higher.And preparation process is simpler, the condition of synthesis is easy to control.
It is following to illustrate that the method using the above-mentioned offer of the present invention prepares urea groups functionalization cadmium ion table with multiple specific examples
The detailed process of face trace adsorbent.
Embodiment 1
The embodiment of the present invention 1 prepares the absorption of urea groups functionalization cadmium ion surface imprint using the aforementioned preparation method
Agent.
Acid activation silica gel：
The hydrochloric acid solution of 100~200 mesh 1g silica gel and a concentration of 8mol/L of 6mL is added in three-necked flask；
The three-necked flask is placed in thermostat water bath, the stir process 9h under the conditions of 50 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber and is dried 15h under the conditions of 90 DEG C, obtains acid activation
Silica gel.
The synthesis of urea groups functionalization cadmium ion surface imprint adsorbent：
1g caddies and 50mL methanol are added in three-necked flask, 20 DEG C of stirring in water bath handle 60min；
2g γ-ureido-propyl trimethoxy silane is added, stir process obtains pre-assembled body；
2g silica gel is added in the pre-assembled body, stir process 12h；
The ammonium persulfate of the epoxychloropropane and 0.1wt% of gross mass 3wt%, stir process 2h is added；
Ethanol solution and second distillation water washing are used respectively；
The hydrochloric acid solution of a concentration of 2mol/L is added, the oscillation treatment 8h under the conditions of 25 DEG C, vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, is dried under the conditions of 50 DEG C for 24 hours, urea groups work(is obtained
It can the ion surface imprinted adsorbent of cadmium.
The preparation process is simpler, and the condition of synthesis is easy to control, is suitble to large-scale production.
Embodiment 2
The embodiment of the present invention 2 prepares the absorption of urea groups functionalization cadmium ion surface imprint using the aforementioned preparation method
Agent.
Acid activation silica gel：
The sulfuric acid solution of 100~200 mesh 10g silica gel and a concentration of 7mol/L of 60mL is added in three-necked flask；
The three-necked flask is placed in thermostat water bath, the 12h at stirring under the conditions of 75 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber and is dried 8h under the conditions of 100 DEG C, obtains acid activation
Silica gel.
The synthesis of urea groups functionalization cadmium ion surface imprint adsorbent：
2g cadmium nitrates and 60mL ethyl alcohol are added in three-necked flask, 35 DEG C of stirring in water bath handle 50min；
4g γ-ureidopropyltriethoxysilane is added, stir process obtains pre-assembled body；
5g silica gel is added in the pre-assembled body, stir process 22h；
The N of gross mass 5wt%, the azodiisobutyronitrile of N- methylene-bisacrylamides and 0.5wt%, stir process is added
5h；
Ethanol solution and second distillation water washing are used respectively；
The salpeter solution of a concentration of 6mol/L is added, the oscillation treatment 7h under the conditions of 30 DEG C, vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 10h is dried under the conditions of 65 DEG C, obtains urea groups work(
It can the ion surface imprinted adsorbent of cadmium.
The preparation process is simpler, and the condition of synthesis is easy to control, is suitble to large-scale production.
Embodiment 3
The embodiment of the present invention 3 prepares the absorption of urea groups functionalization cadmium ion surface imprint using the aforementioned preparation method
Agent.
Acid activation silica gel：
The salpeter solution of 100~200 mesh 25g silica gel and a concentration of 5mol/L of 180mL is added in three-necked flask；
The three-necked flask is placed in thermostat water bath, the stir process 10h under the conditions of 60 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber and is dried 28h under the conditions of 80 DEG C, obtains acid activation
Silica gel.
The synthesis of urea groups functionalization cadmium ion surface imprint adsorbent：
3g cadmium sulfates and 75mL ethylene glycol are added in three-necked flask, 55 DEG C of stirring in water bath handle 40min；
6g γ-ureido-propyl trimethoxy silane is added, stir process obtains pre-assembled body；
9g silica gel is added in the pre-assembled body, stir process 18h；
The azo-bis-iso-dimethyl of the methylene-succinic acid and 1wt% of gross mass 9wt%, stir process 8h is added；
Ethanol solution and second distillation water washing are used respectively；
The hydrochloric acid solution of a concentration of 8mol/L is added, the oscillation treatment 6h under the conditions of 35 DEG C, vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 16h is dried under the conditions of 60 DEG C, obtains urea groups work(
It can the ion surface imprinted adsorbent of cadmium.
The preparation process is simpler, and the condition of synthesis is easy to control, is suitble to large-scale production.
Embodiment 4
The embodiment of the present invention 4 prepares the absorption of urea groups functionalization cadmium ion surface imprint using the aforementioned preparation method
Agent.
Acid activation silica gel：
The phosphoric acid solution of 100~200 mesh 40g silica gel and a concentration of 2mol/L of 260mL is added in three-necked flask；
The three-necked flask is placed in thermostat water bath, the stir process 7h under the conditions of 90 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber and is dried 48h under the conditions of 50 DEG C, obtains acid activation
Silica gel.
The synthesis of urea groups functionalization cadmium ion surface imprint adsorbent：
4g hydrochloric acid cadmium and 90mL n-butanols are added in three-necked flask, 70 DEG C of stirring in water bath handle 30min；
8g γ-ureidopropyltriethoxysilane is added, stir process obtains pre-assembled body；
13g silica gel is added in the pre-assembled body, stir process 15h；
The azobisisoheptonitrile of the diisocyanate and 1.5wt% of gross mass 12wt%, stir process 10h is added；
Ethanol solution and second distillation water washing are used respectively；
The phosphoric acid solution of a concentration of 7mol/L is added, the oscillation treatment 4h under the conditions of 40 DEG C, vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 2h is dried under the conditions of 70 DEG C, obtains urea groups work(
It can the ion surface imprinted adsorbent of cadmium.
The preparation process is simpler, and the condition of synthesis is easy to control, is suitble to large-scale production.
Embodiment 5
The embodiment of the present invention 5 prepares the absorption of urea groups functionalization cadmium ion surface imprint using the aforementioned preparation method
Agent.
Acid activation silica gel：
The hydrochloric acid solution of 100~200 mesh 50g silica gel and a concentration of 3mol/L of 300mL is added in three-necked flask；
The three-necked flask is placed in thermostat water bath, the stir process 6h under the conditions of 100 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber and is dried 40h under the conditions of 65 DEG C, obtains acid activation
Silica gel.
The synthesis of urea groups functionalization cadmium ion surface imprint adsorbent：
5g cadmium sulfates and 100mL isobutanols are added in three-necked flask, 80 DEG C of stirring in water bath handle 20min；
10g γ-ureidopropyltriethoxysilane is added, stir process obtains pre-assembled body；
15g silica gel is added in the pre-assembled body, stir process is for 24 hours；
The azo-bis-iso-dimethyl of the ethylene glycol dimethacrylate and 2wt% of gross mass 15wt% is added, stirs
Mix processing 12h；
Ethanol solution and second distillation water washing are used respectively；
The sulfuric acid solution of a concentration of 8mol/L is added, the oscillation treatment 2h under the conditions of 45 DEG C, vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 10h is dried under the conditions of 55 DEG C, obtains urea groups work(
It can the ion surface imprinted adsorbent of cadmium.
The preparation process is simpler, and the condition of synthesis is easy to control, is suitble to large-scale production.
Urea groups functionalization cadmium ion surface imprint adsorbent prepared by the embodiment of the present invention can be used for Selective Separation cadmium
And/or degradation Cadmium Pollutants On The Chinese.The embodiment of the present invention utilizes the absorption property of Static Adsorption experimental test adsorbent.Specific test side
Method is as follows：
Pollution of chromium solution is added in conical flask with cover, adjusts solution ph to 2~8；
The adsorbent is added in the conical flask with cover；
Then the conical flask with cover is positioned in thermostat water bath, carries out oscillation treatment；
Wherein, the time of the oscillation treatment is 1min~30min, and bath temperature is 20 DEG C~40 DEG C.
Filtered fluid is collected in filtering, surveys the concentration of divalent cadmium in filtered fluid, calculates cadmium pollution solution cadmium ion after processing
Adsorbance.
Divalent cadmium ion initial concentration, pH value of solution, adsorption time and temperature are mainly studied below to the above-mentioned preparation of the present invention
Urea groups functionalization cadmium ion surface imprint adsorbent adsorption effect influence, and comparison ion blotting adsorbent and nonionic
The adsorption effect of trace adsorbent under the same conditions.
Embodiment 6
The embodiment of the present invention 6 prints urea groups functionalization cadmium ion surface using the aforementioned Study on Test Method solution ph
The influence of mark adsorbent adsorption effect.
The cadmium pollution solution for choosing identical divalent cadmium ion initial concentration, adjusts the pH value of solution, is configured to pH value respectively
For 2,3,4,5,6,7,87 pending cadmium pollution solution.
The cadmium pollution solution of 50mL difference pH value is taken to be added in 7 different conical flask with cover, then each tool plug cone
Adsorbent prepared by the 10mg embodiment of the present invention 1 is added in shape bottle, in thermostat water bath under the conditions of 30 DEG C, oscillation treatment
30min, after the completion of reaction, filtering collects filtered fluid, and measures the concentration of divalent cadmium ion in filtered fluid, calculates each cadmium pollution
The adsorbance of solution cadmium ion after processing.As a result see Fig. 3, as shown in Figure 3, work as pH<When 7, adsorbance gradually increases, and works as pH=
When 7, adsorbance reaches maximum.
Embodiment 7
The embodiment of the present invention 7 is using the aforementioned Study on Test Method divalent cadmium ion initial concentration to urea groups function cadmium
The influence of ion surface imprinted adsorbent adsorption effect.
First prepare divalent cadmium ion initial concentration be respectively 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L,
8 parts of 60mg/L, 70mg/L, 80mg/L pending cadmium pollution solution.
It takes the cadmium pollution solution of 50mL various concentrations to be added in 8 different conical flask with cover respectively, adjusts pH value of solution
Value is 7, and adsorbent prepared by the 10mg embodiment of the present invention 2 is then added in each conical flask with cover, in thermostat water bath in
Under the conditions of 30 DEG C, oscillation treatment 30min, after the completion of reaction, filtering collects filtered fluid, and measures divalent cadmium ion in filtered fluid
Concentration, calculate the adsorbance of each cadmium pollution solution cadmium ion after processing.As a result Fig. 4 is seen, as shown in Figure 4, with initial cadmium
The increase of ion concentration, urea groups functionalization cadmium ion surface imprint adsorbent are presented increase tendency to the adsorbance of cadmium, arrive first
Initial concentration of cadmium ions is 60mg/L, reaches maximum.
Embodiment 8
The embodiment of the present invention 8 prints urea groups functionalization cadmium ion surface using the aforementioned Study on Test Method adsorption time
The influence of mark adsorbent adsorption effect.
The cadmium pollution solution for choosing identical divalent cadmium ion initial concentration, the pH value for adjusting solution are 7.
The above-mentioned cadmium pollution solution of 10 parts of 50mL is taken to be added in 10 different conical flask with cover, then each tool plug cone
Adsorbent prepared by the 10mg embodiment of the present invention 3 is added in shape bottle, in thermostat water bath under the conditions of 30 DEG C, 1min~
Different time progress oscillation treatments is pressed within the scope of 30min respectively, after the completion of reaction, filtering collects filtered fluid, and measures filtering
The concentration of divalent cadmium ion in liquid calculates the adsorbance of each cadmium pollution solution cadmium ion after processing.As a result Fig. 5 is seen, by Fig. 5 institutes
Show, the rate of adsorption quickly, can reach adsorption equilibrium in 10min.
Embodiment 9
The embodiment of the present invention 9 inhales urea groups functionalization cadmium ion surface imprint using the aforementioned Study on Test Method temperature
The influence of attached dose of adsorption effect.
The cadmium pollution solution for choosing identical divalent cadmium ion initial concentration, the pH value for adjusting solution are 7.
The above-mentioned cadmium pollution solution of 3 parts of 50mL is taken to be added in 3 different conical flask with cover, then each tool plug taper
Adsorbent prepared by the 10mg embodiment of the present invention 4 is added in bottle, respectively in 20 DEG C, 30 DEG C, 40 DEG C of conditions in thermostat water bath
Under, oscillation treatment 30min, after the completion of reaction, filtering collects filtered fluid, and measures the concentration of divalent cadmium ion in filtered fluid, counts
Calculate the adsorbance of each cadmium pollution solution cadmium ion after processing.As a result see Fig. 5, as shown in Figure 5, under the conditions of 30 DEG C, adsorbance
Maximum reaches as high as 79.94mg/g.
Embodiment 10
The embodiment of the present invention 10 compares trace adsorbent and non-trace under the same terms using the aforementioned test method and inhales
Attached dose of adsorption effect.
First prepare divalent cadmium ion initial concentration be respectively 5mg/L, 10mg/L, 15mg/L, 20mg/L, 25mg/L,
Each two groups of 30mg/L, 35mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L pending cadmium pollution solution, adjusts solution
PH value is 7.
The cadmium pollution solution of 50mL various concentrations is taken to be added in different conical flask with cover respectively, one of which cadmium pollution
The adsorbent of the preparation of the 10mg embodiment of the present invention 5 is separately added into solution, another group is separately added into the absorption of 10mg nonionic traces
Agent, then in thermostat water bath under the conditions of 30 DEG C, oscillation treatment 30min, after the completion of reaction, filtered fluid is collected in filtering, and
The concentration for measuring divalent cadmium ion in filtered fluid calculates the adsorbance of each cadmium pollution solution cadmium ion after processing.As a result see figure
6, as shown in Figure 6, the adsorbance of trace adsorbent prepared by the present invention is significantly larger than the adsorbance of non-trace adsorbent.
It is right first the present invention provides a kind of preparation method and application of urea groups functionalization cadmium ion surface imprint adsorbent
Carrier silica gel carries out acid activation, and a large amount of hydroxyl is generated on its surface；Undertake γ-urea groups third of coupling agent and function monomer effect
Base trimethoxy silane or γ-ureidopropyltriethoxysilane and inorganic cadmium salt are with 2:1 ratio is dissolved in organic solvent
Form the pre-assembled body of complex compound；Activated silica gel is added, pre-assembled body is grafted to Silica Surface；It is crosslinked synthesis print by causing
Mark polymer, elution vacuum drying, obtains the urea groups functionalized surface trace adsorbent for having matching hole to cadmium ion.By quiet
The performance of the adsorbent is studied in state adsorption test, the results showed that the adsorbent is with the up to adsorbance of 79.94mg/g and quickly
Adsorption Kinetics, the cadmium ion surface imprint adsorbent in the present invention can be used for the separation and removal of cadmium ion, inhales
Attached speed is fast, adsorption equilibrium, and high selectivity can be reached in 10min, minimizing technology is simple, easily operated.
Above-described specific implementation mode has carried out further the purpose of the present invention, technical solution and advantageous effect
It is described in detail, it should be understood that the foregoing is merely the specific implementation mode of the present invention, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of urea groups functionalization cadmium ion surface imprint adsorbent, which is characterized in that the method includes：
The inorganic cadmium salts of 1~5g and organic solvent are added in three-necked flask, 20 DEG C~80 DEG C stirring in water bath processing 20~
60min；
Coupling agent is added, stir process obtains pre-assembled body；
2~15g silica gel is added in the pre-assembled body, stir process 12h~48h；
Crosslinking agent and initiator, stir process 2h~12h is added；
Ethanol solution and second distillation water washing are used respectively；
The acid solution of a concentration of 2mol/L~8mol/L is added, oscillation treatment 2h~8h under the conditions of 25 DEG C~45 DEG C, vacuum is taken out
Filter obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is positioned in vacuum drying chamber, 2h~for 24 hours is dried under the conditions of 50 DEG C~70 DEG C, is obtained
Urea groups functionalization cadmium ion surface imprint adsorbent；
Wherein, the mass ratio of inorganic cadmium salt and coupling agent is 1:2；
The coupling agent is γ-ureido-propyl trimethoxy silane and one kind or more in γ-ureidopropyltriethoxysilane
Kind；
The amount of the crosslinking agent accounts for the 3%~15% of gross mass；
The silica gel is the silica gel handled by acid activation, specially：
The acid solution of the every 1~50g silica gel of 100~200 mesh and a concentration of 2mol/L~8mol/L of 6mL~300mL is added to three
In mouth flask；
The three-necked flask is placed in thermostat water bath, stir process 6h~12h under the conditions of 50 DEG C~100 DEG C；
Vacuum filtration obtains sediment；
It is 6~7 that the sediment, which is washed repeatedly with redistilled water to filtrate pH,；
Sediment after washing is put into vacuum drying chamber, 8h~48h is dried under the conditions of 50 DEG C~100 DEG C, is obtained
The silica gel of acid activation.
2. according to the method described in claim 1, it is characterized in that, the inorganic cadmium salt is caddy, cadmium nitrate or cadmium sulfate.
3. according to the method described in claim 1, it is characterized in that, the organic solvent is methanol, ethyl alcohol, ethylene glycol, positive third
Alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol, n-amyl alcohol, sec-amyl alcohol, tertriary amylo alcohol, isoamyl alcohol, n-hexyl alcohol and ring
It is one or more in hexanol.
4. according to the method described in claim 1, it is characterized in that, the crosslinking agent is ethylene glycol dimethacrylate, ring
Oxygen chloropropane, N,N methylene bis acrylamide, 4- urocanic acids ethyl ester, methylene-succinic acid, divinylbenzene and two are different
It is one or more in cyanate.
5. according to the method described in claim 1, it is characterized in that, the initiator is azodiisobutyronitrile, two different heptan of azo
It is one or more in nitrile, azo-bis-iso-dimethyl, ammonium persulfate and potassium peroxydisulfate；The amount of the initiator accounts for gross mass
0.1%~2%.
6. according to the method described in claim 1, it is characterized in that, the acid solution is that hydrochloric acid solution, salpeter solution, sulfuric acid are molten
One kind in liquid and phosphoric acid.
7. a kind of purposes of adsorbent as described in claim 1, which is characterized in that the adsorbent is used for Selective Separation cadmium
And/or degradation Cadmium Pollutants On The Chinese, include the following steps：
Cadmium pollution solution is added in conical flask with cover, adjusts solution ph to 7；
The adsorbent is added in the conical flask with cover；
Then the conical flask with cover is positioned in thermostat water bath, carries out oscillation treatment；
Wherein, the time of the oscillation treatment is 1min~30min, and bath temperature is 20 DEG C~40 DEG C.
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