CN104959130A - Resin with functions of chelating and adsorbing as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses resin with functions of chelating and adsorbing as well as a preparation method and application thereof. The preparation method of the resin with the functions of chelating and adsorbing comprises the following steps: (1) soaking chloromethylated beads in N,N-dimethylformamide (DMF) which is used as a reaction solvent till the chloromethylated beads are fully swelled; (2) adding methyl piperazine (MPP) which is used as a ligand into a product obtained in the step (1), and stirring and reacting for 10 to 12 hours at 100 to 120 DEG C under the condition of nitrogen protection, wherein the ratio of the amount of the methyl piperazine (MPP) to the amount of -CH2Cl substance in the chloromethylated beads is (3.8 to 4.2) to 1; and (3) filtering the product obtained in the step (2) to obtain a filter cake, soaking and washing the filter cake for 3 to 4 times with N,N-dimethylformamide (DMF) which is used as the reaction solvent, then washing the filter cake with distilled water, acetone, diethyl ether and absolute ethyl alcohol, and drying the filter cake in vacuum at 40 to 60 DEG C till the filter cake is constant in weight to prepare the resin with the functions of chelating and adsorbing. The resin with the functions of chelating and adsorbing has the characteristics of selective adsorption, excellent adsorption property and reusability on Mn(VII) in the aqueous solution.

Description

Chelating adsorption function resin, its preparation method and application

Technical field

The present invention relates to a kind of preparation method of chelating adsorption function resin, be specifically related to a kind of to Mn in the aqueous solution (VII), to there is the preparation method of modification chelating function polymeric adsorbent that selective absorption, absorption property are good, can reuse.

Background technology

Suitability for industrialized production potassium permanganate (KMnO ₄) process in, the residue after water drop is got is called manganese mud.Manganese mud goes out of use and is not only the waste of promoter manganese, and causes alkali pollution and " red water " pollution.The generation of red water is because the absorption of manganese mud, the potassium manganate solution generation disproportionated reaction of carrying secretly generate caused by liquor potassic permanganate.When finding leaching manganese mud in experimental study, manganese and iron all have higher leaching rate, therefore, when producing manganese goods by method for separating and concentrating from leachate, also face the problem of iron ion interference.Conventional method for separating and concentrating has many kinds: as membrane separation process, solvent extraction, electrochemical reducing, chemical deposition method, ion-exchange-resin process, chelate adsorption concentration method etc.The Master Cost that membrane separation process uses is higher; The operating process of solvent extraction is very loaded down with trivial details, and the effumability of organic solvent, toxicity and high cost also make its practical application be restricted; The energy consumption of electrochemical reducing is too high; Chemical deposition method is comparatively common, but its precipitating reagent used is often expensive, and when processing the metal ion of low concentration poor effect; Ion exchange resin treatment method is simple to operate, and cost is lower but selective poor; Adsorption capacity is large, enrichment times is high because having for chelating adsorption functional material, selective good, easy and simple to handle, resin easily regenerates and the advantage such as acid and alkali-resistance and the trace metal ion be widely used in the selective separation enrichment aqueous solution.

Summary of the invention

In order to solve the problems of the technologies described above, the invention provides a kind of chelating adsorption function resin, its preparation method and application, have the advantages that preparation technology is simple, with low cost, and the chelating adsorption function resin that the present invention prepares there is higher selective adsorption capacity to Mn (VII) ion.

In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of chelating adsorption function resin, with chlorine ball for parent, methyl piperazine (MPP) is part, carry out modification to the benzyl on chlorine ball, chlorine ball is macroporous type chloroethyl crosslinked polystyrene microballoon; Comprise the following steps:

1), using chlorine ball the N as reaction dissolvent is immersed in, in N-dimethylformamide (DMF), until chlorine ball is fully swelling;

2), in step 1) gains in add methyl piperazine (MPP) as part, under the condition of nitrogen protection at 100 ~ 120 DEG C stirring reaction 10 ~ 12 hours; Wherein, methyl piperazine (MPP) and-CH in chlorine ball ₂the ratio of the amount of substance of Cl is 3.8 ~ 4.2:1;

3), filtration step 2) gains, obtain filter cake, filter cake is used as the N of reaction dissolvent, N-dimethylformamide (DMF) washing by soaking 3 ~ 4 times, then uses distilled water, acetone, ether, absolute ethanol washing successively; 40 ~ 60 DEG C of vacuum drying, to constant weight, obtain chelating adsorption function resin.

Preferably, step 1) in: the amount ratio of chlorine ball and N, N-dimethylformamide is: the N of 1mg chlorine ball/1 ~ 2ml, N-dimethylformamide, and soak time is 22 ~ 26 hours.

Preferably, step 2) in, reaction temperature is 120 DEG C.

Preferably, step 2) in, the reaction time is 10 hours.

The present invention also provides the chelating prepared by said method adsorption function resin.

The chelating adsorption function resin prepared by said method of the present invention is for adsorbing septivalency manganese ion.Wherein, adsorption conditions is pH value is 5.0.

The chelating adsorption function resin (hereinafter referred to as PS-MPP) that employing the inventive method is prepared and obtained, carry out following experiment:

One, heavy metal ion adsorbed experiment:

Adsorption experiment carries out in constant temperature oscillator, accurately take in PS-MPP to the 100ml iodine flask of a certain amount of (being such as 15.0mg), add certain volume 25ml respectively, the NaAc_HAc buffer solution (hereinafter referred to as HAc-NaAc cushioning liquid) of certain pH value (such as pH value is 5.0) soaks 24h, then add the heavy metal ion titer prepared of a certain amount of (being such as 5ml) respectively, under agitation carry out adsorption operations.Residual metal ions concentration in determination and analysis aqueous phase at regular intervals, until balance.Adsorbance (Q is calculated with following formula _e) and distribution ratio (D):

$Q_e=\frac{(C_o-C_e)V}{m}---\left(1\right)$

$D=\frac{Q_e}{C_e}---\left(2\right)$

Q in formula _efor the adsorbance (mgg of PS-MPP during balance ^-1); C _oand C _ebe respectively the initial concentration (mgmL of metal ion in aqueous phase ^-1) and equilibrium concentration (mgmL ^-1); M is the quality (g) of PS-MPP; V is liquid phase volume (mL), refers to heavy metal ion titer and volume of buffer solution sum.

Two, desorption experiment

Accurately take the metal ion solution 5ml that 3 parts of 15.0mg PS-MPP add 0.700mg/ml respectively, certain pH value (pH value is 5.0) HAc-NaAc cushioning liquid adds 25ml, cumulative volume is that 30ml vibrates absorption under the rotating speed of 298K, 100r/min, after adsorption equilibrium.By resin filter, use HAc-NaAc cushioning liquid (pH value is 5.0) respectively, distilled water washs 3 times, as in iodine flask after low temperature drying, add 30ml concentration and be respectively 0.5mol/l, 1.0mol/l, 2.0mol/l, the NaOH stripping liquid of 5.0mol/l, 6.0mol/l, measures the concentration of heavy metal ion in solution after constant temperature oscillation to balance.The desorption efficiency of adsorbent is calculated as follows:

$E\left(\%\right)=\frac{\left(C_d{V}_d\right)}{(C_0-C_e)V}\×100\%---\left(3\right)$

C in formula _dfor the equilibrium concentration (mgmL of metal ion in strippant ^-1); V _dfor stripping liquid volume (mL) used.C _oand C _ebe respectively the initial concentration (mgmL of metal ion in aqueous phase ^-1) and equilibrium concentration (mgmL ^-1); V is liquid phase volume (mL).

The present invention, relative to prior art, has following advantage:

1, the raw material of chelating adsorption function resin that the present invention obtains is chlorine ball, has higher mechanical strength and physical stability wide material sources, cheap, has obvious economic benefit.

2, the present invention utilizes chemical graft process by the modification of chlorine ball, makes it have larger chemical stability, and enhances opposing acid, the ability of alkali and organic solvent and adsorption capacity thereof.

3, the PS-MPP that the inventive method is obtained has higher selective absorption to Mn (VII), and adsorbance is large, and adsorption rate is fast, does not substantially adsorb Fe (III).

4, the chelating adsorption function resin chemical stability that obtains of the present invention is good, can wash-out, reduces secondary pollution, is convenient to reuse.

5, the preparation method of chelating adsorption function resin of the present invention is easy and simple to handle, and productive rate is high.

Accompanying drawing explanation

Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.

Fig. 1 is reaction principle figure of the present invention;

Fig. 2 is that reaction mol ratio is on the impact of chlorine ball function base conversion ratio;

Fig. 3 is the impact of reaction temperature on chlorine ball function base conversion ratio;

Fig. 4 is the impact of reaction time on chlorine ball function base conversion ratio;

Fig. 5 be under different pH value PS-MPP on the impact of the adsorption capacity of metal ions M n (VII), Fe (III);

Fig. 6 be at different time and temperature PS-MPP on the impact of the adsorbance of metal ions M n (VII).

Detailed description of the invention

Describe the present invention further below in conjunction with specific embodiment, but content of the present invention is not limited to this.

Remarks: the washing in following examples is washs with distilled water.

Embodiment 1

The preparation method's of a chelating adsorption function resin preparation method, comprises the following steps:

1), under room temperature, the chlorine ball accurately taking 20.0 ㎎, in the three-necked bottle of 100ml, adds N, N-dimethylformamide (DMF) 30ml, and soaked overnight (about 24 hours) makes chlorine ball fully swelling;

2), in step 1) gains in add methyl piperazine (MPP) as part, methyl piperazine (MPP) and-CH on chlorine ball ₂the ratio of the amount of substance of Cl is 4:1, keeps the reaction temperature of 120 DEG C to stir (rotating speed is 100r/min) and react 12 hours under the protective condition of nitrogen;

3), reaction terminate after by step 2) gains filter, the filter cake N of gained, N-dimethylformamide (DMF) washing by soaking 3 ~ 4 times (each consumption is 40ml), then distilled water, acetone, ether, absolute ethanol washing is used successively, 4 times repeatedly (each, the consumption of distilled water is 40ml, the consumption of acetone is 40ml, the consumption of ether is 40ml, the consumption of absolute ethyl alcohol be 40ml); 50 DEG C of vacuum drying, to constant weight, obtain chelating adsorption function resin (referred to as PS-MPP).

Wherein, macroporous type chloroethyl crosslinked polystyrene microballoon (also name macroporous type chloroethyl crosslinked polystyrene, PS-CH ₂cl, hereinafter referred to as chlorine ball) belong to prior art, such as can purchased from Chemical Plant of Nankai Univ. etc., the degree of cross linking 8%.

Experiment 1

Accurately taking every part is that 4 parts, the chlorine ball of 20.0 ㎎ is placed in 100ml iodine flask, and the DMF adding 30ml soaks 24h makes chlorine ball fully swelling, then adds a certain amount of methyl piperazine as the part (-CH in methyl piperazine and chlorine ball respectively ₂the ratio of the material amount of Cl is respectively 2:1,3:1,4:1,5:1), under nitrogen protection condition at 120 DEG C stirring reaction 10h.After reaction terminates, filter, the filter cake of gained DMF washing by soaking 3 ~ 4 times, then use distilled water, acetone, ether, absolute ethyl alcohol cyclic washing for several times (such as 4 times) successively, at 50 DEG C, vacuum drying is to constant weight.According to following formula computing function base conversion ratio, draw the optimum synthesis condition of resin of the present invention.Function base conversion ratio is calculated as follows:

$N\%=\frac{1\×{\mathrm{aM}}_N{F}_{0x}}{1000+1\×F_0\mathrm{\Δ}Mx}---\left(4\right)$

In formula, N% is resin contains nitrogen amount after the synthesis that records of elementary analysis, and a is containing atom N number in per molecule part; M _nfor the molal weight of atom N; F ₀(5.39mmol/g) be chlorine ball function base (-CH ₂cl) content; Δ M is resin gain in weight (g/mol) after 1mol function base transforms; X is the function base conversion ratio of resin.

Experimental result as shown in Figure 2, according to Fig. 2, is learnt: when mol ratio is lower, and the function base conversion ratio of resin increases with the rising of mol ratio; But along with the continuation of mol ratio increases, resin function base conversion ratio has no obvious rising, and this may be because the avtive spot of parent fully contacts the state of reaching capacity with part, so continue to improve the conversion ratio that concentration is also difficult to improve function base.So, finally determine that the optimum response mol ratio of PS-MPP is 4:1; I.e. methyl piperazine (MPP) and-CH in chlorine ball ₂ratio the best of the amount of substance of Cl is 4:1.

Experiment 2

Accurately taking every part is that 5 parts, the chlorine ball of 20.0 ㎎ is placed in 100ml iodine flask, and the DMF adding 30ml soaks 24h makes chlorine ball fully swelling, then adds a certain amount of methyl piperazine as the part (-CH in methyl piperazine and chlorine ball respectively ₂the ratio of the material amount of Cl is respectively 4:1), stirring reaction 10h at 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C respectively under nitrogen protection condition.After reaction terminates, leached by resin, with DMF washing by soaking 3 ~ 4 times, then use distilled water, acetone, ether, absolute ethyl alcohol cyclic washing for several times (such as 4 times) successively, at 50 DEG C, vacuum drying is to constant weight.According to following formula computing function base conversion ratio, draw the optimum synthesis condition of resin.

Wherein, the account form of function base conversion ratio is with reference to described in experiment 1.The result of this experiment as shown in Figure 3.

According to Fig. 3, learn: when reaction temperature is lower, the conversion ratio of resin function base raises with the rising of temperature; But after reaching certain temperature, continue raised temperature and can not continue the conversion ratio significantly improving function base.The consideration of Comprehensive Experiment condition and combined coefficient, finally determines that the optimum synthesising temperature of PS-MPP is 120 DEG C.

Experiment 3

Accurately taking every part is that 5 parts, the chlorine ball of 20.0 ㎎ is placed in 100ml iodine flask; the DMF adding 30ml soaks 24h makes chlorine ball fully swelling; add a certain amount of methyl piperazine as part (methyl piperazine is respectively 4:1 with the ratio of the material amount of-CH2Cl in chlorine ball) more respectively, stirring reaction 6h, 8h, 10h, 12h at 120 DEG C respectively under nitrogen protection condition.After reaction terminates, leached by resin, with DMF washing by soaking 3 ~ 4 times, then use distilled water, acetone, ether, absolute ethyl alcohol cyclic washing for several times (such as 4 times) successively, at 50 DEG C, vacuum drying is to constant weight.

Wherein, the account form of function base conversion ratio is with reference to described in experiment 1.The result of this experiment as shown in Figure 4.

According to Fig. 4, learn: when reaction temperature is constant, the conversion ratio of resin function base increase in time and raising; But after exceeding certain hour, continue time expand and can not continue the conversion ratio significantly improving function base, decrease on the contrary.The consideration of Comprehensive Experiment condition and combined coefficient, finally determines that the best generated time of PS-MPP is 10h.

Experiment 4

Accurately take the PS-MPP resin 7 parts that every part is 15.0mg gained of the present invention and be placed in 100ml iodine flask, the corresponding pH=3.0 adding 20ml respectively, pH=3.5, pH=4.0, pH=4.5, pH=5.0, pH=5.5, pH=6.0, after the HAc-NaAc cushioning liquid immersion 24h of pH=6.5, every part adds 5.0mL, Mn (VII) solion (for adopting potassium permanganate formulated) of 0.700mg/mL and 5.0mL, constant temperature oscillator is placed under Fe (III) solion (for the adopting ferric trichloride formulated) 298K of 0.700mg/mL, with the rotating speed constant temperature jolting of 100r/min, residual metal ions concentration in determination and analysis aqueous phase at regular intervals, until balance.As stated above, can show that pH is on the impact of modified chelating function resin on septivalency manganese ion and ferric ion absorption property.Acquired results as shown in Figure 5.

According to Fig. 5, learn: modified chelating function resin (PS-MPP resin) the optimal adsorption pH value to Mn (VII) solion is 5.0, can from substantially not adsorbing Fe (III) containing selective absorption Mn (VII) the mixed solution of Fe (III), Mn (VII) simultaneously.

Experiment 5

Accurately take the PS-MPP resin 3 parts of the gained of the present invention that every part is 30.0mg, add respectively in 50ml HAc-NaAc cushioning liquid (pH is 5.0) and soak after 24 hours, add 10.0ml, Mn (VII) solion (for adopting potassium permanganate formulated) of 0.700mg/mL, adsorb with the speed constant temperature oscillation of 100r/min at 15 DEG C, 25 DEG C, 35 DEG C respectively, the measured in solution concentration of metal ions that taking-up quantitative after separated in time is a small amount of, until adsorption equilibrium.Acquired results as shown in Figure 6.

According to Fig. 6, learn: all larger in the rate of adsorption of incipient stage resin; Along with the carrying out of absorption, speed reduces gradually; Finally reach balance.And along with the adsorbance of rising resin heavy metal ion Mn (VII) of temperature also increases, PS-MPP resin of the present invention is 40h to the time of equilibrium adsorption of septivalency manganese ion as seen from Figure 6.

In sum, the optimum synthesis condition of chelating adsorption function resin of the present invention (PS-MPP resin) is :-the CH in methyl piperazine and chlorine ball ₂the ratio of the amount of substance of Cl is 4:1, and synthesis reaction temperature is 120 DEG C, and synthesising reacting time is 10 hours, and the chlorine ball function base conversion ratio of gained is 88.68%; Optimal adsorption condition is: optimal adsorption pH value is 5.0, and the adsorption effect of gained is: 47.5mg/g.

Experiment 6

Accurately take PS-MPP3 part that every part is 15.0mg gained of the present invention, every part of Mn (VII) solion adding 0.700mg/mL (for adopting potassium permanganate formulated) 5ml, HAc-NaAc cushioning liquid (pH is 5.0) 25ml, cumulative volume is that 30ml is in 15 DEG C, vibration absorption under the rotating speed of 100r/min, after adsorption equilibrium; By resin filter, use HAc-NaAc (pH is 5.0) respectively, distilled water wash successively 3 times (each, the consumption of HAc-NaAc is 40ml, the consumption of distilled water is 40ml), add 30ml concentration and be respectively 0.5mol/l, 1.0mol/l, 2.0mol/l, the NaOH stripping liquid of 5.0mol/l, 6mol/l, resolves completely and surveys concentration of metal ions.Acquired results is as shown in table 1.

The desorption efficiency of PS-MPP under table 1 different N aOH concentration

Comparative example 1

Change the methyl piperazine resin as sorbing material in embodiment 1 into shitosan (CTS).The other the same as in Example 1.

Detected according to the method for experiment 4 by CTS, its optimal adsorption condition is: optimal adsorption pH value is 3.0, and the optimal adsorption effect of gained to Mn (VII) is: 11mg/g.Adsorbance is far below the PS-MPP resin in embodiment 1.

Comparative example 2

The methyl piperazine as part in embodiment 1 is made into 4-AA (AATP), 2-amido-6-chloropurine (ACP), 2-mercaptobenzothiazole (MPTZ), Lamotrigine (LMTG), modification is carried out to chlorine ball, the other the same as in Example 1.

4 kinds of material modified methods according to experiment 4 in comparative example are detected, they to Mn (VII) all without obvious adsorption effect.

Above-described embodiment does not limit the present invention in any way, and the technical scheme that the mode that every employing is equal to replacement or equivalent transformation obtains all drops in protection scope of the present invention.

Claims (8)

1. a preparation method for chelating adsorption function resin, is characterized in that: with chlorine ball for parent, and methyl piperazine is part, carries out modification to the benzyl on chlorine ball, and described chlorine ball is macroporous type chloroethyl crosslinked polystyrene microballoon; Comprise the following steps:

1), using chlorine ball the N as reaction dissolvent is immersed in, in N-dimethylformamide, until chlorine ball is fully swelling;

2), in the gains of step 1), add methyl piperazine as part, under the condition of nitrogen protection at 100 ~ 120 DEG C stirring reaction 10 ~ 12 hours, wherein ,-the CH in described methyl piperazine and chlorine ball ₂the ratio of the amount of substance of Cl is 3.8 ~ 4.2:1;

3), filtration step 2) gains, obtain filter cake, filter cake is used as the N of reaction dissolvent, N-dimethylformamide washing by soaking 3 ~ 4 times, then uses distilled water, acetone, ether, absolute ethanol washing successively; 40 ~ 60 DEG C of vacuum drying, to constant weight, obtain chelating adsorption function resin.

2. preparation method according to claim 1, is characterized in that:

In described step 1): the amount ratio of chlorine ball and N, N-dimethylformamide is: the N of 1mg chlorine ball/1 ~ 2ml, N-dimethylformamide, soak time is 22 ~ 26 hours.

3. preparation method according to claim 1, is characterized in that:

Described step 2) in ,-the CH in described methyl piperazine and chlorine ball ₂the ratio of the amount of substance of Cl is 4:1.

4. preparation method according to claim 1, is characterized in that:

Described step 2) in, reaction temperature is 120 DEG C.

5. preparation method according to claim 1, is characterized in that:

Described step 2) in, the reaction time is 10 hours.

6. a chelating adsorption function resin, is characterized in that, is obtained by the preparation method described in any one of claim 1 to 5.

7. the application of chelating adsorption function resin according to claim 6, is characterized in that, for adsorbing septivalency manganese ion.

8. application according to claim 7, is characterized in that, adsorption conditions is pH value is 5.0.