CN105236506B - A kind of method for reclaiming zinc ion in willemite stone waste water - Google Patents
A kind of method for reclaiming zinc ion in willemite stone waste water Download PDFInfo
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- CN105236506B CN105236506B CN201510581652.3A CN201510581652A CN105236506B CN 105236506 B CN105236506 B CN 105236506B CN 201510581652 A CN201510581652 A CN 201510581652A CN 105236506 B CN105236506 B CN 105236506B
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- chlorine ball
- zinc ion
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Abstract
The present invention discloses a kind of method for reclaiming zinc ion in willemite stone waste water, including：（1）Chlorine ball is immersed in the N as reaction dissolvent, N dimethylformamides, until chlorine ball is fully swelled；（2）In step（1）Gains in add the p-aminobenzoic acid as part, add catalyst, under 80 120oC reaction temperature, heating stirring is reacted 10 hours under nitrogen protection.（3）Filtration step（2）Gains, obtain filter cake, filter cake is used as to the N of reaction dissolvent, N dimethylformamides washing by soaking to cleaning solution is colourless, then with distillation water washing, then uses NaOH aqueous solution soakings, with distillation water washing, washed successively with absolute ethyl alcohol, acetone, ether again, in being dried in vacuo under 50oC, obtain adsorption function resin；（4）The dried resin 15mg of precise, add acetic acid sodium acetate buffer soaked overnight, after after willemite waste water natural sedimentation, take the resin and remaining acetic acid sodium acetate buffer added in 50~100mL supernatants after being swelled, 10h takes out resin and washed with 0.5~2mol/L HCl, and solution is zinc ion solution after washing.
Description
Technical field
The present invention relates to resin-made is standby and application process, more particularly to a kind of willemite stone waste water to processing in zinc ion have
There is high efficiency to reclaim, absorption property is good, repeat the synthetic resin method utilized and reclaim zinc ion in willemite stone waste water
Method.
Background technology
With continuing to develop for society, industrial expansion is also constantly improving, and the thing followed is exactly various industrial wastewaters
Process problem.Present people start increasingly influence of the concern heavy metal pollution to human body and ecology of water.Due to heavy metal
Pollutant is difficult to degrade in the environment, can be progressively enriched with, finally accumulated in animal and plant body by food chain, enable concentration into hundred
On thousandfold increase, many environmental hazard events are relevant with heavy metal pollution, are one of the pollutants for endangering human maximum.
It is nowadays to compare a popular research topic that heavy metal is reclaimed from the heavy metal wastewater thereby of low concentration.Common
Recovery method has chemical precipitation method, oxidation-reduction method, electrolysis, physisorphtion and biological adsorption method etc., but they
Cost is often higher or treatment effect is undesirable or technology is still immature, and some processing products can also cause secondary pollution.
Compared to these methods, ion-exchange-resin process is swift in response, wide adaptation range, and eluting rate is high, residue is stable again without secondary
Pollution, can remove a variety of ions, can be used with repeated regeneration, long working life, operating cost is relatively low, in industry
Obtain more and more widely using in wastewater treatment process.
Ion-exchange-resin process has the advantages that above-mentioned, but still has a maximum defect, that is, existing method is inhaled
The attached time is universal longer, although adsorbance can reach 200mg/g even close to 300mg/g, but it is most of need one to two day,
Seem that time cost is too high for reclaiming the serious zinc of pollution level, inefficiency.And present quick adsorption method adsorbance is general
All over not high, adsorbance can only hover in 70-80mg/g, it is impossible to meet demand.And handle in willemite stone waste water containing micro
The metal ions such as Fe, Mn, if directly discharge will caused environmental pollution.So urgent need is a kind of can to replace their method
Quickly to be reclaimed to zinc ion, with reach cost recovery, economize on resources, the purpose of environmental protection.
The content of the invention
The present invention provides a kind of synthetic resin and preparation method thereof, and the synthetic resin obtained using this method is to processing silicon zinc
Zinc ion has higher efficiency to reclaim in ore waste water.
In order to solve the above-mentioned technical problem, the present invention provide reclaim willemite stone waste water in zinc ion method include with
Lower step following scheme：
(1) chlorine ball is immersed in as in the DMF of reaction dissolvent, until chlorine ball is fully swelled, it is described
Chlorine ball is the crosslinked chloromethylated polystyrene bead of macroporous type；
(2) p-aminobenzoic acid as part is added in the gains of step (1), catalyst is added, in 80-120
DEG C reaction temperature under, under nitrogen protection heating stirring react 10 hours, rotating speed be 100~300r/min, wherein, the chlorine
The reaction mol ratio of ball and p-aminobenzoic acid is 1:3~1:5；
(3) gains of filtration step (2), obtain filter cake, and filter cake is used as to the N of reaction dissolvent, N- dimethyl formyls
Amine washing by soaking to be colourless, then with distillation water washing, then uses NaOH aqueous solution soakings to cleaning solution, with distillation water washing, then
Washed successively with absolute ethyl alcohol, acetone, ether, in being dried in vacuo at 50 DEG C, obtain adsorption function resin；
(4) the dried resin 15mg of precise, adds pH=4.5 NaAc_HAc buffer solution, and immersion 24 is small
When, gains (including resin after being swelled and surplus is added in 50~100mL supernatants after after willemite waste water natural sedimentation, taking
Remaining NaAc_HAc buffer solution), resin washing is taken out after 10h, is washed with 0.5~2mol/L HCl, solution is after washing
Zinc ion solution.
It is preferred that in step 1) in, the amount ratio of chlorine ball and DMF is：1.5mg chlorine ball/1ml N,
Dinethylformamide.
It is preferred that in step 2) in, temperature is 80 DEG C.
It is preferred that in step 2) in, the reaction mol ratio of chlorine ball and p-aminobenzoic acid is 1:4.
It is preferred that in step 2) in, speed of agitator is 200r/min.
It is preferred that in step 4) in, eluted using 1mol/L HCl.
The present invention has the advantage that relative to prior art：
(1) raw material that the present invention is used is chlorine ball, with higher mechanical strength and physical stability wide material sources, price
It is cheap, with obvious economic benefit；
(2) synthetic resin that the present invention is obtained there is higher efficiency to reclaim and return zinc in processing willemite stone waste water
Receive function strong, adsorption rate is fast；
(3) synthetic resin that the present invention is obtained can be desorbed effectively using HCl solution, and the resin rate of recovery is high, be saved
Cost benefit is big, and the heavy metal of desorption can also be utilized by enriching and recovering, so as to effectively save resource；
(4) part of the present invention is that the material of new exploration is easy to operation to produce novel absorption material, adsorption function resin
Preparation method is simple to operate.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 show the reaction principle figure of the present invention；
Fig. 2 show influence of the reaction temperature to synthetic resin function base conversion ratio；
Fig. 3 show influence of the reaction mol ratio to synthetic resin function base conversion ratio；
Fig. 4 show absorption of the synthetic resin to zinc ion under condition of different pH；
Fig. 5 show absorption of the synthetic resin to zinc ion under different temperatures；
Fig. 6 show kinetic curve of the synthetic resin to the absorption of zinc ion under different temperatures.
Embodiment
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.Wherein, following examples
In washing be to be washed with distilled water.
Embodiment 1
(1) it is accurate to weigh 60.0mg chlorine balls, in the three-necked bottle for moving into 100mL, add 40mL and be used as the N of reaction dissolvent, N-
In dimethylformamide (DMF), it is dipped to chlorine ball and is fully swelled, wherein, chlorine ball is the crosslinked chloromethylated polystyrene of macroporous type
Bead；
(2) p-aminobenzoic acid (PABA) as part, chlorine ball and p-aminophenyl are added in the gains of step (1)
The reaction mol ratio of formic acid is 1:4, catalyst is added, under 80 DEG C of reaction temperature, stirring reaction 10 is small under nitrogen protection
When, rotating speed is 200r/min；
(3) after reflection terminates, the gains of filtration step (2) obtain filter cake, filter cake are used as to the N of reaction dissolvent, N-
Dimethylformamide washing by soaking to cleaning solution is colourless, then with distillation water washing, then uses NaOH aqueous solution soakings, washes,
Washed successively with absolute ethyl alcohol, acetone, ether again, in being dried in vacuo at 50 DEG C, obtain adsorption function resin.
In this, determined with infrared spectrum (FTIR), elementary analysis (EA) synthesis adsorption function resin structure and
Functional group content, infers that the synthesis mechanism of adsorption function resin is as shown in Figure 1.
Comparative example 1
Make the reaction dissolvent in embodiment 1 into Isosorbide-5-Nitrae-dioxane, toluene, methyltetrahydrofuran, dimethyl sulfoxide, remaining
The step of be the same as Example 1, the synthetic reaction of p-aminobenzoic acid part and chlorine ball is inquired into, 1 is the results are shown in Table.
The elementary analysis of resin under the different solvents of table 1
According to overall conversion of the resin in five kinds of solvents in table 1, it is determined that synthesized by part of p-aminobenzoic acid
Resin, its optimum solvent be DMF.
Comparative example 2
Reacted under conditions of making 80 DEG C of reaction temperature in the step of embodiment 1 (2) into 100 DEG C, 120 DEG C, remaining
The step of be the same as Example 1, influence of the reaction temperature to synthetic resin function base conversion ratio is inquired into, as a result as shown in Figure 2.
In this, because DMF boiling point is 152.8 DEG C, therefore the synthesis temperature scope of PABA (p-aminobenzoic acid) resin is selected
It is selected as 80-120 DEG C.As shown in Figure 2, when reaction temperature is less than 100 DEG C, the function base conversion ratio of resin rises with the raising of temperature
It is high.This is probably, because rise reaction temperature can lift part to the speed of the reactivity site diffusion on chlorine ball, to improve
The concentration of avtive spot part, promotes reaction to carry out.For the synthesis of PABA resins, when temperature is from when rising to 100 DEG C for 80 DEG C,
Function base conversion ratio is slightly lifted, but not substantially, and when temperature rises to 120 DEG C from 100 DEG C again, function base conversion ratio base
This temperature.The consideration of Comprehensive Experiment condition, economic condition and combined coefficient, the optimum synthesising temperature for determining resin is 80 DEG C.
Comparative example 3
By in the step of embodiment 1 (2), the reaction mol ratio of p-aminobenzoic acid and chlorine ball is by 4:1 is changed to 3:1、5:1, its
The step of remaining be the same as Example 1, influence of the reaction mol ratio to synthetic resin function base conversion ratio is inquired into, as a result as shown in Figure 3.Really
The optimum response mol ratio for determining p-aminobenzoic acid and chlorine ball is 4：1.
In summary analyze, it is determined that the optimal reaction condition of resins synthesis, such as table 2.
The optimum synthesis condition of the resin of table 2
Embodiment two
Experiment 1
Weigh the synthetic resin that 7 parts of 15.0mg present invention obtain respectively to be placed in iodine flask, then respectively in iodine flask
Add pH=3, pH=3.5, pH=4.0, pH=4.5, pH=5, pH=5.5 and pH=6 NaAc_HAc buffer solution
25mL soaks 24 hours in iodine flask, then, takes the willemite stone waste water modulated in right amount to make Zn2+Concentration 2mg/ml, Zhi Houqu
Synthesis is determined after solution 5mL, constant temperature oscillation 10 hours under conditions of r=200r/min, T=298K, balance to be adsorbed respectively
Saturated adsorption capacity of the resin to metal zinc ion.
Wherein, adsorbance (q is calculated with following formulae) and distribution ratio (D)：
Q in formulaeFor the equilibrium adsorption capacity (mg/g) of resin；CoAnd CeThe initial concentration of metal ion respectively in aqueous phase
And equilibrium concentration (mg/mL) (mg/mL)；M is resin quality (g)；V0For metal ion solution volume (mL).
As shown in figure 4, when pH value of solution changes in the range of 3~5.5, absorption of the p-aminobenzoic acid chlorine ball to zinc ion
Amount reaches maximum in pH=4.5, therefore experiment is carried out most preferably under conditions of pH=4.5 cushioning liquid.
Experiment 2
Accurate 3 parts weigh synthetic resin that the 30.0mg present invention obtains in iodine flask, add pH=4.5 acetic acid-vinegar
Sour sodium cushioning liquid 50mL, soaks 24 hours, then adds the 2mg/ml willemite stone waste water solution 10ml containing zinc ion,
Respectively in T=288K, 298K, 308K rotating speeds are constant temperature oscillation under conditions of r=200r/min.At regular intervals determine zinc from
The concentration of son, until adsorption equilibrium.
As shown in Figure 5, it is that synthetic resin can be with temperature to the yield of zinc ion in T=288K-298K in temperature range
The rise of degree and it is significantly raised, but when temperature more than T=298K after, synthetic resin is begun to decline to zinc ion yield, and
And illustrate in T=298K that for one of optimum condition of this experiment maximal absorptive capacity is 184mg/g by Fig. 6.So present invention choosing
T=298K is selected as the temperature conditionss tested later.
Experiment 3
It is accurate to weigh synthetic resin that the 15.0mg present invention obtains in iodine flask, add pH=4.5 Acetic acid-sodium acetate
Cushioning liquid 25mL, soaks 24 hours；Then the willemite stone waste water solution 5ml of 2mg/ml zinc ion is added, in r=
Constant temperature oscillation under conditions of 200r/min, T=298K is until after adsorption equilibrium, by resin filter, adding 30ml concentration is respectively
Concentration is surveyed after 0.1mol/L, 0.5mol/L, 1mol/L and 2mol/L HCl, desorption completely.
According to experimental data using HCl concentration as independent variable, PABA resins are listed to the desorption efficiency of zinc ion for dependent variable
Desorption efficiency of the PABA resins under the conditions of various concentrations HCl, as a result as shown in table 3.
Desorption efficiency of the synthetic resin of table 3 under the conditions of various concentrations HCl
| HCl concentration (mol/L) | Desorption efficiency % |
| 0.1 | 82.44 |
| 0.5 | 98.66 |
| 1 | 100 |
| 2 | 100 |
As shown in Table 3, desorption agent concentration is to influence the key factor of synthetic resin desorption performance.The HCl of various concentrations is molten
The desorption effect of liquid is different, and the desorption efficiency of 0.5mol/L HCl solution is 98.66% in four kinds of various concentrations eluant, eluents, although
Concentration higher 1mol/L or 2mol/L desorption effect is more preferable, but for economy, 0.5mol/L desorption efficiency is
Enough.
Above-mentioned absorption zinc ion standard liquid experiment understands that the dried resin 15mg of precise takes 50~100mL silicon
Resin is added in zinc ore wastewater supernatant fluid, 10h takes out resin washing, washed with 0.5~2mol/L HCl, and solution is zinc after washing
Solion.
Experiment 4
In order to exclude influence of other heavy metal ion to adsorption effect, in 5ml willemite stone waste water solution respectively
Add concentration and be 2mg/ml iron (Fe), manganese (Mn), zinc (Zn) each 1ml of solion, and add the synthesis tree that the present invention is obtained
Fat is adsorbed, balance to be adsorbed, 10 times of measurements of sampling dilution before and after absorption, to each ionic adsorption amount such as table 4 below：
Absorption of the PABA chelating resins of table 4 to zinc
| Different metal element | Concentration (ppm) before absorption | Concentration (ppm) after absorption |
| Zn | 40 | 2.2 |
| Fe | 40 | 39.2 |
| Mn | 40 | 39.5 |
As shown in Table 4, the novel chelate resin that the present invention is provided is larger to the adsorbance of zinc ore treatment fluid, and to wherein
Its his ion is hardly adsorbed.
Comparative example 2-1
Chelating resin in embodiment 2 is changed to 4-- aminopyridine resins, remaining is equal to embodiment 2.To zinc ion
Adsorption time is 40h, to the adsorbance 58.4mg/g of zinc ion.
Comparative example 2-2
Chelating resin in embodiment 2 is changed to Amino phosphonic acid resin, remaining is equal to embodiment 2.Suction to zinc ion
Attached amount is 109.2mg/g (static state), and the adsorption time to zinc ion is 42h, 2.0molL-1HCl makees eluant, eluent, and eluting rate is
98%.
Comparative example 2-3
Chelating resin in embodiment 2 is changed to macro-porous phosphonic acid resin, remaining is equal to embodiment 2.Suction to zinc ion
Attached amount is 64.8mg/g (static state) and 58.2mg/g (dynamic), adsorption time 8h.
It can be seen from above-mentioned comparative example, the recovery rate and the aspect PABA resins of yield two of comprehensive zinc ion have very
Obvious advantage.
Above-described embodiment does not limit the present invention in any way, every to be obtained by the way of equivalent substitution or association's conversion
Technical scheme it is within the scope of the present invention.
Claims (6)
1. a kind of method for reclaiming zinc ion in willemite stone waste water, it is characterised in that comprise the following steps：
（1）Chlorine ball is immersed in as in the DMF of reaction dissolvent, until chlorine ball is fully swelled, the chlorine ball
For the crosslinked chloromethylated polystyrene bead of macroporous type；
（2）In step（1）Gains in add the p-aminobenzoic acid as part, catalyst is added, 80-120oC's
Under reaction temperature, under nitrogen protection heating stirring react 10 hours, rotating speed be 100~300r/min, wherein, the chlorine ball with
The reaction mol ratio of p-aminobenzoic acid is 1:3~1:5；
（3）Filtration step（2）Gains, obtain filter cake, by filter cake be used as reaction dissolvent DMF soak
Foam washing is washed to cleaning solution to be colourless, then with distillation water washing, then uses NaOH aqueous solution soakings, with distillation water washing, then successively
Washed with absolute ethyl alcohol, acetone, ether, in being dried in vacuo under 50oC, obtain adsorption function resin；
（4）The dried resin 15mg of precise, adds the NaAc_HAc buffer solution of pH=4.5, soaks 24 hours, treats
After willemite waste water natural sedimentation, take the resin and remaining Acetic acid-sodium acetate added in 50~100mL supernatants after being swelled slow
Rush taking-up resin after solution, 10h to be washed with 0.5~2mol/L HCl, solution is zinc ion solution after washing.
2. according to the method described in claim 1, it is characterised in that：Step（1）In, the use of chlorine ball and DMF
Measuring ratio is：1.5mg chlorine ball/1ml N,N-dimethylformamide.
3. according to the method described in claim 1, it is characterised in that：Step（2）In, the reaction temperature is 80oC.
4. according to the method described in claim 1, it is characterised in that：Step（2）In, the chlorine ball and p-aminobenzoic acid it is anti-
It is 1 to answer mol ratio:4.
5. according to the method described in claim 1, it is characterised in that：Step（2）In, speed of agitator is 200 r/min.
6. according to the method described in claim 1, it is characterised in that：Step（4）In, washed most using 1mol/L HCl
It is good.
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| CN201510581652.3A CN105236506B (en) | 2015-09-14 | 2015-09-14 | A kind of method for reclaiming zinc ion in willemite stone waste water |
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| CN201510581652.3A CN105236506B (en) | 2015-09-14 | 2015-09-14 | A kind of method for reclaiming zinc ion in willemite stone waste water |
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| CN105236506A CN105236506A (en) | 2016-01-13 |
| CN105236506B true CN105236506B (en) | 2017-08-25 |
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| JP5637708B2 (en) * | 2010-03-19 | 2014-12-10 | 戸田工業株式会社 | Fluorine ion-containing wastewater treatment method with fluorine adsorbent |
| CN101967209B (en) * | 2010-10-20 | 2012-11-07 | 南京大学 | N-acetylethylenediamine chelate resin and preparation method thereof |
| CN102861556B (en) * | 2012-09-08 | 2014-05-14 | 浙江工商大学 | Preparation method of chelating adsorption function resin |
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