CN104959130B - Chelate adsorption function resin, its preparation method and application - Google Patents
Chelate adsorption function resin, its preparation method and application Download PDFInfo
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- CN104959130B CN104959130B CN201510411705.7A CN201510411705A CN104959130B CN 104959130 B CN104959130 B CN 104959130B CN 201510411705 A CN201510411705 A CN 201510411705A CN 104959130 B CN104959130 B CN 104959130B
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- chlorine ball
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Abstract
The invention discloses one kind chelating adsorption function resin, its preparation method and application, comprise the following steps：1）, chlorine ball is immersed in the N as reaction dissolvent, N-dimethylformamide（DMF）In, until chlorine ball is fully swelled；2）, in step 1）Gains in add the methyl piperazine as part（MPP）, in stirring reaction 10 ~ 12 hours at 100 ~ 120 DEG C under conditions of nitrogen protection；Wherein, methyl piperazine（MPP）With the CH in chlorine ball2The ratio between Cl amount of material is 3.8 ~ 4.2：1；3）, filtration step 2）Gains, obtain filter cake, filter cake be used as to the N of reaction dissolvent, N-dimethylformamide（DMF）Washing by soaking 3 ~ 4 times, is then washed with distilled water, acetone, ether, absolute ethyl alcohol successively；40 ~ 60 DEG C are dried under vacuum to constant weight, obtain chelating adsorption function resin.The chelating adsorption function resin that the present invention is provided is to Mn in the aqueous solution（Ⅶ）The features such as with selective absorption, good absorption property, repeatable utilization.
Description
Technical field
The present invention relates to a kind of preparation method for chelating adsorption function resin, and in particular to a kind of to Mn in the aqueous solution
(VII) have that selective absorption, absorption property be good, the repeatable modification chelating function polymeric adsorbent utilized preparation method.
Background technology
Industrialized production potassium permanganate (KMnO4) during, the residue after being leached through water is referred to as manganese mud.Manganese mud goes out of use
The waste of promoter manganese is not only, and causes alkali pollution and " red water " pollution.The generation of red water is due to the absorption of manganese mud, entrainment
Potassium manganate solution occur disproportionated reaction generation liquor potassic permanganate caused by.When leaching manganese mud is found in experimental study, manganese and iron
Higher leaching rate is respectively provided with, therefore, when producing manganese product by method for separating and concentrating from leachate, iron ion is also faced with and does
The problem of disturbing.Conventional method for separating and concentrating has many kinds：As membrane separation process, solvent extraction, electrochemical reducing, chemistry are heavy
Drop method, ion-exchange-resin process, chelate adsorption concentration method etc..The Master Cost that membrane separation process is used is higher；Solvent extraction
The operating process of method is extremely cumbersome, and effumability, toxicity and the high cost of organic solvent are also restricted its practical application；Electricity
The energy consumption of chemical reduction method is too high；Chemical deposition method is relatively conventional, but its precipitating reagent used is often expensive, and processing compared with
Effect is not good during the metal ion of low concentration；Ion exchange resin treatment method is simple to operate, and cost is relatively low but selectivity is poor；Chela
Adsorption functional material is closed because with adsorption capacity is big, enrichment times are high, selectivity good, easy to operate, resin easily regenerates and resistance to
The advantages of soda acid and be widely used in the trace metal ion in the selective separation enrichment aqueous solution.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides a kind of chelating adsorption function resin, its preparation method and application,
With preparation technology it is simple, it is with low cost the characteristics of, and the chelating adsorption function resin for preparing of the present invention is to Mn (VII)
Ion has higher selective adsorption capacity.
In order to solve the above-mentioned technical problem, the present invention provides a kind of preparation method for chelating adsorption function resin, with chlorine ball
For parent, methyl piperazine (MPP) is part, and the benzyl on chlorine ball is modified, and chlorine ball is that the crosslinking of macroporous type chloromethylation is poly-
Phenylethylene micro ball；Comprise the following steps：
1), chlorine ball is immersed in the N as reaction dissolvent, N-dimethylformamide (DMF), until chlorine ball is fully swelled；
2), in step 1) gains in add the methyl piperazine (MPP) as part, nitrogen protection under conditions of in
Stirring reaction 10~12 hours at 100~120 DEG C；Wherein, methyl piperazine (MPP) and-CH in chlorine ball2The amount of Cl material it
Than for 3.8~4.2：1；
3), filtration step 2) gains, obtain filter cake, filter cake be used as to the N of reaction dissolvent, N-dimethylformamide
(DMF) washing by soaking 3~4 times, are then washed with distilled water, acetone, ether, absolute ethyl alcohol successively；40~60 DEG C of vacuum drying
To constant weight, chelating adsorption function resin is obtained.
It is preferred that step 1) in：The amount ratio of chlorine ball and N, N-dimethylformamide is：1mg chlorine ball/1~2ml N, N-
Dimethylformamide, soak time is 22~26 hours.
It is preferred that step 2) in, reaction temperature is 120 DEG C.
It is preferred that step 2) in, the reaction time is 10 hours.
The present invention also provides the chelating adsorption function resin prepared by the above method.
The chelating adsorption function resin prepared by the above method of the present invention is used to adsorb septivalency manganese ion.Wherein,
Adsorption conditionses are that pH value is 5.0.
The chelating adsorption function resin (hereinafter referred to as PS-MPP) being prepared using the inventive method, is carried out as follows
Experiment：
First, heavy metal ion adsorbed experiment：
Adsorption experiment is carried out in constant temperature oscillator, accurately weighs the PS-MPP of a certain amount of (being, for example, 15.0mg) extremely
In 100ml iodine flasks, certain volume 25ml, the Acetic acid-sodium acetate buffering of certain pH value (being, for example, that pH value is 5.0) are separately added into
Solution (hereinafter referred to as HAc-NaAc cushioning liquid) soaks 24h, is then respectively adding preparing for a certain amount of (being, for example, 5ml)
Heavy metal ion titer, adsorption operations are carried out under agitation.At regular intervals determine analysis aqueous phase in residual metal from
Sub- concentration, until balance.Adsorbance (Q is calculated with following formulae) and distribution ratio (D)：
Q in formulaePS-MPP adsorbance (mgg during for balance-1)；CoAnd CeMetal ion is initial respectively in aqueous phase
Concentration (mgmL-1) and equilibrium concentration (mgmL-1)；M is PS-MPP quality (g)；V is liquid phase volume (mL), refers to a huge sum of money
Belong to ion titer and volume of buffer solution sum.
2nd, desorption experiment
Accurately weigh the metal ion solution 5ml that 3 parts of 15.0mg PS-MPP are separately added into 0.700mg/ml, certain pH value
(pH value is 5.0) HAc-NaAc cushioning liquid adds 25ml, and cumulative volume is that 30ml inhales in vibration under 298K, 100r/min rotating speed
It is attached, after adsorption equilibrium.By resin filter, respectively with HAc-NaAc cushioning liquid (pH value is 5.0), distillation water washing 3 times, low temperature
As in iodine flask after drying, it is respectively 0.5mol/l, 1.0mol/l, 2.0mol/l, 5.0mol/l to add 30ml concentration,
6.0mol/l sodium hydroxide stripping liquid, constant temperature oscillation determines the concentration of heavy metal ion in solution to after balancing.Adsorbent
Desorption efficiency is calculated as follows：
C in formuladFor the equilibrium concentration (mgmL of metal ion in strippant-1)；VdFor stripping liquid volume (mL) used.
CoAnd CeInitial concentration (the mgmL of metal ion respectively in aqueous phase-1) and equilibrium concentration (mgmL-1)；V is liquid phase volume
(mL)。
The present invention has the advantage that relative to prior art：
1st, the raw material of chelating adsorption function resin produced by the present invention is chlorine ball, steady with higher mechanical strength and physics
Qualitative wide material sources, it is cheap, with obvious economic benefit.
2nd, the present invention makes it have larger chemical stability using chemical graft process by chlorine ball modification, and enhance to
The ability and its adsorption capacity of antiacid, alkali and organic solvent.
3rd, PS-MPP made from the inventive method has higher selective absorption to Mn (VII), and adsorbance is big, adsorption rate
It hurry up, Fe (III) do not adsorbed substantially.
4th, chelating adsorption function resin chemical stability produced by the present invention is good, can elute, reduce secondary pollution, be easy to
Reuse.
5th, the preparation method of chelating adsorption function resin of the invention is easy to operate, and yield is high.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the reaction principle figure of the present invention；
Fig. 2 is the influence for reacting mol ratio to chlorine ball function base conversion ratio；
Fig. 3 is influence of the reaction temperature to chlorine ball function base conversion ratio；
Fig. 4 is influence of the reaction time to chlorine ball function base conversion ratio；
Fig. 5 be under different pH value PS-MPP to metal ions M n (VII), the influence of Fe (III) adsorption capacity；
Fig. 6 is the different time influences of PS-MPP to metal ions M n (VII) adsorbance with a temperature of.
Embodiment
The present invention is further depicted as with reference to specific embodiment, but present disclosure is not limited to this.
Remarks：Washing in following examples is to be washed with distilled water.
Embodiment 1
A kind of preparation method for the preparation method for chelating adsorption function resin, comprises the following steps：
1) 20.0 ㎎ chlorine ball, at room temperature, is accurately weighed in 100ml three-necked bottle, adds N, N-dimethylformamide
(DMF) 30ml, soaked overnight (about 24 hours) makes chlorine ball fully be swelled；
2), in step 1) gains in add the methyl piperazine (MPP) as part, methyl piperazine (MPP) and chlorine ball
Upper-CH2The ratio between Cl amount of material is 4：1,120 DEG C of reaction temperature stirring is kept under the protective condition of nitrogen, and (rotating speed is
100r/min) react 12 hours；
3) by step 2 after, reaction terminates) gains filtered, the filter cake N of gained, N-dimethylformamide
(DMF) washing by soaking 3~4 times (each consumption is 40ml), is then washed with distilled water, acetone, ether, absolute ethyl alcohol successively
Wash, 4 times repeatedly (every time, the consumption of distilled water is that 40ml, the consumption of acetone are that 40ml, the consumption of ether are 40ml, absolute ethyl alcohol
Consumption be 40ml)；50 DEG C are dried under vacuum to constant weight, must chelate adsorption function resin (referred to as PS-MPP).
Wherein, macroporous type chloroethyl crosslinked polystyrene microballoon (also name macroporous type chloroethyl crosslinked polystyrene,
PS-CH2Cl, hereinafter referred to as chlorine ball) belong to prior art, such as being purchased from Chemical Plant of Nankai Univ., the degree of cross linking 8%.
Experiment 1
Accurately weigh 4 parts of the chlorine ball that every part is 20.0 ㎎ to be placed in 100ml iodine flasks, adding 30ml DMF immersions 24h makes
Chlorine ball is fully swelled, then is separately added into a certain amount of methyl piperazine (methyl piperazine and the-CH in chlorine ball as part2Cl thing
Mass ratio is respectively 2:1、3:1、4:1、5:1), under nitrogen protective condition at 120 DEG C stirring reaction 10h.Reaction terminates
Afterwards, filter, the filter cake of gained DMF washing by soaking 3~4 times, then successively with distilled water, acetone, ether, absolute ethyl alcohol repeatedly
Washing for several times (such as 4 times), constant weight is dried under vacuum at 50 DEG C.According to following formula computing function base conversion ratio, the present invention is drawn
Resin optimum synthesis condition.Function base conversion ratio is calculated as follows：
N% is resin nitrogen content after the synthesis that elementary analysis is measured in formula, and a is the number of atom containing N in per molecule part；MN
For the molal weight of N atoms；F0(5.39mmol/g) is chlorine ball function base (- CH2Cl) content；Δ M is after 1mol functions base is converted
Resin gain in weight (g/mol)；X is the function base conversion ratio of resin.
Experimental result is as shown in Fig. 2 according to Fig. 2, learn：When mol ratio is relatively low, the function base conversion ratio of resin is with rubbing
The rise of your ratio and increase；But with the continuation increase of mol ratio, resin function base conversion ratio has no significantly raised, and this is probably
Saturation state is reached because the avtive spot of parent is fully contacted with part, also is difficult to improve function so continuing raising concentration
The conversion ratio of base.So, the final optimum response mol ratio for determining PS-MPP is 4：1；I.e. in methyl piperazine (MPP) and chlorine ball
- CH2The ratio between Cl amount of material most preferably 4：1.
Experiment 2
Accurately weigh 5 parts of the chlorine ball that every part is 20.0 ㎎ to be placed in 100ml iodine flasks, adding 30ml DMF immersions 24h makes
Chlorine ball is fully swelled, then is separately added into a certain amount of methyl piperazine (methyl piperazine and the-CH in chlorine ball as part2Cl thing
Mass ratio is respectively 4:1), under nitrogen protective condition respectively 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130
Stirring reaction 10h at DEG C.After reaction terminates, resin is filtered out, with DMF washing by soaking 3~4 times, distilled water, third are then used successively
Ketone, ether, absolute ethyl alcohol cyclic washing for several times (such as 4 times), constant weight are dried under vacuum at 50 DEG C.According to following formula computing function
Base conversion ratio, draws the optimum synthesis condition of resin.
Wherein, the calculation of function base conversion ratio is with reference to described in experiment 1.The result of this experiment is as shown in Figure 3.
According to Fig. 3, learn：When reaction temperature is relatively low, the conversion ratio of resin function base is raised with the rise of temperature；But
Reach after certain temperature, continuing rise temperature can not continue to significantly improve the conversion ratio of function base.Comprehensive Experiment condition and conjunction
Into the consideration of efficiency, the final optimum synthesising temperature for determining PS-MPP is 120 DEG C.
Experiment 3
Accurately weigh 5 parts of the chlorine ball that every part is 20.0 ㎎ to be placed in 100ml iodine flasks, adding 30ml DMF immersions 24h makes
Chlorine ball is fully swelled, then is separately added into a certain amount of methyl piperazine (thing of methyl piperazine and the-CH2Cl in chlorine ball as part
Mass ratio is respectively 4:1), stirring reaction 6h, 8h, 10h, 12h at 120 DEG C respectively under nitrogen protective condition.Reaction knot
Shu Hou, resin is filtered out, and with DMF washing by soaking 3~4 times, is then washed repeatedly with distilled water, acetone, ether, absolute ethyl alcohol successively
(such as 4 times) for several times are washed, constant weight is dried under vacuum at 50 DEG C.
Wherein, the calculation of function base conversion ratio is with reference to described in experiment 1.The result of this experiment is as shown in Figure 4.
According to Fig. 4, learn：When reaction temperature is constant, the conversion ratio of resin function base is raised with the increase of time；But
After certain time, the continuation extension time can not continue to significantly improve the conversion ratio of function base, decrease on the contrary.It is comprehensive real
The consideration of condition and combined coefficient is tested, the final optimal generated time for determining PS-MPP is 10h.
Experiment 4
Every part is accurately weighed to be placed in 100ml iodine flasks for 7 parts of PS-MPP resins obtained by the 15.0mg present invention, it is right respectively
20ml pH=3.0, pH=3.5, pH=4.0, pH=4.5, pH=5.0, pH=5.5, pH=6.0, pH=6.5 should be added
After HAc-NaAc cushioning liquid immersion 24h, every part of addition 5.0mL, 0.700mg/mL Mn (VII) solion (are using high
Potassium manganate is formulated) and 5.0mL, 0.700mg/mL Fe (III) solion (be using ferric trichloride be formulated)
It is placed in constant temperature oscillator, is shaken with 100r/min rotating speed constant temperature under 298K, determines residual in analysis aqueous phase at regular intervals
Remaining concentration of metal ions, until balance.As stated above, pH can be drawn to modified chelating function resin to septivalency manganese ion
With the influence of ferric ion absorption property.Acquired results are as shown in Figure 5.
According to Fig. 5, learn：Modified chelating function resin (PS-MPP resins) is to the optimal of Mn (VII) solion
It is 5.0 to adsorb pH value, can be from simultaneously containing selective absorption Mn (VII) in Fe (III), Mn (VII) mixed solution to Fe
(III) do not adsorb substantially.
Experiment 5
3 parts of PS-MPP resins obtained by every part of present invention for 30.0mg are accurately weighed, 50ml HAc-NaAc are separately added into
After being soaked 24 hours in cushioning liquid (pH is 5.0), 10.0ml is added, 0.700mg/mL Mn (VII) solion is (to use
Potassium permanganate is formulated), adsorbed respectively at 15 DEG C, 25 DEG C, 35 DEG C with 100r/min speed constant temperature oscillation, interval is certain
The a small amount of solution of quantitative taking-up determines concentration of metal ions after time, until adsorption equilibrium.Acquired results are as shown in Figure 6.
According to Fig. 6, learn：Incipient stage resin the rate of adsorption all than larger；With the progress of absorption, speed is gradually
Reduction；Finally reach balance.And the adsorbance with the rise resin heavy metal ion Mn (VII) of temperature also increases, by
Fig. 6 can be seen that the PS-MPP resins of the present invention are 40h to the time of equilibrium adsorption of septivalency manganese ion.
In summary, the optimum synthesis condition of chelating adsorption function resin of the invention (PS-MPP resins) is：Methyl piperazine
Piperazine and the-CH in chlorine ball2The ratio between Cl amount of material is 4:1, synthesis reaction temperature is 120 DEG C, and synthesising reacting time is 10 small
When, the chlorine ball function base conversion ratio of gained is 88.68%；Optimal adsorption condition is：Optimal adsorption pH value is 5.0, the suction of gained
Attached effect is：47.5mg/g.
Experiment 6
Accurately weigh every part for 15.0mg the present invention obtained by PS-MPP3 part, every part add 0.700mg/mL Mn (VII) from
Sub- solution (being to be formulated using potassium permanganate) 5ml, HAc-NaAc cushioning liquid (pH is 5.0) 25ml, cumulative volume is 30ml
Adsorbed in being vibrated under 15 DEG C, 100r/min rotating speed, after adsorption equilibrium；By resin filter, with HAc-NaAc, (pH is respectively
5.0), distilled water washs 3 times (every time, HAc-NaAc consumption is 40ml, and the consumption of distilled water is 40ml) successively, adds 30ml
Concentration is respectively 0.5mol/l, 1.0mol/l, 2.0mol/l, 5.0mol/l, and 6mol/l sodium hydroxide stripping liquid, parsing is complete
After survey concentration of metal ions.Acquired results are as shown in table 1.
PS-MPP desorption efficiency under the different NaOH concentrations of table 1
Comparative example 1
Methyl piperazine resin in embodiment 1 as sorbing material is changed to chitosan (CTS).The other the same as in Example 1.
CTS is detected that its optimal adsorption condition is according to the method for experiment 4：Optimal adsorption pH value is 3.0, gained
Optimal adsorption effect to Mn (VII) is：11mg/g.Adsorbance is far below the PS-MPP resins in embodiment 1.
Comparative example 2
The methyl piperazine as part in embodiment 1 is made to 4-AA (AATP), 2- amino -6- chlorine into fast
Purine (ACP), 2-mercaptobenzothiazole (MPTZ), Lamotrigine (LMTG), are modified, the other the same as in Example 1 to chlorine ball.
4 kinds in the comparative example material modified methods according to experiment 4 are detected, they are to Mn (VII) without obvious
Adsorption effect.
Above-described embodiment does not limit the present invention in any way, every to be obtained by the way of equivalent substitution or equivalent transformation
Technical scheme all fall within protection scope of the present invention.
Claims (5)
1. a kind of preparation method for chelating adsorption function resin, it is characterized in that：Using chlorine ball as parent, methyl piperazine is part, right
Benzyl on chlorine ball is modified, and the chlorine ball is macroporous type chloroethyl crosslinked polystyrene microballoon；Comprise the following steps：
1), chlorine ball is immersed in the N as reaction dissolvent, N-dimethylformamide, until chlorine ball is fully swelled；
2), in step 1) gains in add the methyl piperazine as part, nitrogen protection under conditions of in 100~120
Stirring reaction 10~12 hours at DEG C, wherein, the methyl piperazine and the-CH in chlorine ball2The ratio between Cl amount of material be 3.8~
4.2：1；
3), filtration step 2) gains, obtain filter cake, filter cake be used as to the N of reaction dissolvent, N-dimethylformamide immersion is washed
Wash 3~4 times, then washed successively with distilled water, acetone, ether, absolute ethyl alcohol；40~60 DEG C are dried under vacuum to constant weight, obtain
Chelating adsorption function resin for adsorbing septivalency manganese ion；
Wherein, the step 1) in：The amount ratio of chlorine ball and N, N-dimethylformamide is：1mg chlorine ball/1~2ml N, N-bis-
Methyl nitrosourea, soak time is 22~26 hours.
2. preparation method according to claim 1, it is characterized in that：
The step 2) in, the methyl piperazine and the-CH in chlorine ball2The ratio between Cl amount of material is 4：1.
3. preparation method according to claim 1, it is characterized in that：
The step 2) in, reaction temperature is 120 DEG C.
4. preparation method according to claim 1, it is characterized in that：
Adsorption conditionses are that pH value is 5.0.
5. one kind chelating adsorption function resin, it is characterized in that, obtained as the preparation method described in any one of Claims 1-4.
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| CN109384872B (en) * | 2018-10-12 | 2021-04-27 | 上海应用技术大学 | Chelate resin and preparation method and application thereof |
| CN111269340B (en) * | 2020-03-31 | 2020-12-29 | 台州学院 | Chelate resin with 1-methanesulfonyl piperazine as ligand and preparation method and application thereof |
| CN111269338B (en) * | 2020-03-31 | 2021-04-13 | 台州学院 | Chelate resin with 4-piperidyl piperidine as ligand and preparation method and application thereof |
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| CN102861556A (en) * | 2012-09-08 | 2013-01-09 | 浙江工商大学 | Preparation method of chelating adsorption function resin |
| CN104610483A (en) * | 2015-02-05 | 2015-05-13 | 浙江工商大学 | Preparation method of chelating functional resin with selective adsorption to Hg(II) |
| CN104628906A (en) * | 2015-02-05 | 2015-05-20 | 浙江工商大学 | Preparation method of chelate resin capable of selectively adsorbing Hg (II) |
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| CN102861556A (en) * | 2012-09-08 | 2013-01-09 | 浙江工商大学 | Preparation method of chelating adsorption function resin |
| CN104610483A (en) * | 2015-02-05 | 2015-05-13 | 浙江工商大学 | Preparation method of chelating functional resin with selective adsorption to Hg(II) |
| CN104628906A (en) * | 2015-02-05 | 2015-05-20 | 浙江工商大学 | Preparation method of chelate resin capable of selectively adsorbing Hg (II) |
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