CN1188456C - Chelate resin and its synthesis method - Google Patents
Chelate resin and its synthesis method Download PDFInfo
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- CN1188456C CN1188456C CNB021290520A CN02129052A CN1188456C CN 1188456 C CN1188456 C CN 1188456C CN B021290520 A CNB021290520 A CN B021290520A CN 02129052 A CN02129052 A CN 02129052A CN 1188456 C CN1188456 C CN 1188456C
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- resin
- intermediate product
- macroporous resin
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- metal ion
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Abstract
The present invention discloses chelating resin and a synthetic method thereof. The synthetic method of the chelating resin comprises the following steps: water solubility heavy metal ion adsorbing agents are coated on the surface of a basal body of conventional macroporous resin by a chemical method; the adsorbing agents are mutually crosslinked by a chemical crosslinking agent, and therefore, the water solubility heavy metal ion adsorbing agents are firmly attached to the surface of the macroporous resin to obtain the chelating resin. The chelating resin can fully play the characteristics of the large specific surface area and the strong metal adsorbing agent complex capability of a macroporous polymer carrier and has the advantages of good adsorption kinetics performance, large absorption capacity and easy elution. The chelating resin has wide application prospect in the aspects of the purification of heavy metal industrial waste water, the enrichment of precious metal, etc., and the chelating resin can be used for the absorption and the purification of acidic gas, such as HCl, SO2, H2S, etc., in environmental air and industrial waste gas.
Description
Technical field
The present invention relates to the ion exchange resin preparing technical field, particularly a kind of resin and synthetic method.
Background technology
Existing multiple at present is that material is made the resin appearance with the styrene resin.As U.S. Pat A-4002564 and USA-4818773, disclose a kind of synthetic method that is used for the macropore amine alkylphosphonic acid carboxylic acid resin of waste water metal ion removing, Chinese patent 871037599 discloses the method for a kind of polystyrene resin and ethylpyridine prepared in reaction new function resin.These method agents useful for same toxicity are bigger, prepared resin property instability, and kinetics of adsorption is relatively poor, and loading capacity is little, and the regenerative elution difficulty influences practical effect.
Summary of the invention
The object of the present invention is to provide a kind of stable performance, the kinetics of adsorption performance is good, loading capacity is big, regenerative elution is easy resin and synthetic method thereof.
To achieve these goals, the present invention proposes a kind of resin, this resin is to adopt the slightly acidic macroporous resin as carrier, heavy metal ion is gone up in its exchange, utilize the avidity between heavy metal ion and the water-soluble macromolecule metal ion adsorbent again, with the surface of adsorbents adsorb, and then make it securely attached to making on the matrix resin by linking agent at macroporous resin.The macroporous polymer carrier is selected slightly acidic polystyrene type macroporous resin for use, or slightly acidic polymethyl acrylate class macroporous resin, or slightly acidic polymethylmethacrylate class macroporous resin, or slightly acidic polypropylene nitrile macroporous resin; Metal salt solution can be the salts solution of copper, lead, zinc, cadmium, mercury, gold, chromium, uranium or other heavy metals; The water-soluble macromolecule metal ion adsorbent is selected polymine for use, and its molecular weight is 500～75000; Linking agent select for use oxalic dialdehyde, polyaldehyde such as suceinic aldehyde, glutaraldehyde a kind of or several mixture in them.
This resin is synthetic can be realized by following steps:
1) hydrolysis makes the transition.Promptly under 30-100 ℃ of condition, it is 4%～30% strong alkali aqueous solution that the macropore weakly acidic cation-exchange resin is put into concentration, makes it transform into the Na type by the H type, intermediate product I;
2) introduce the bridge ion.Being about to intermediate product I, to put into concentration be that 1%～35% heavy metallic salt solution carries out ion exchange reaction, make its positively charged ion fully be converted into heavy metal ion, thereby make matrix resin have avidity metal absorbent, intermediate product II;
3) sorbent material chemistry " coating ".At normal temperatures promptly, it is that 0.5%～50% metal ion adsorbent polyethyleneimine: amine aqueous solution reacts that intermediate product II is put into concentration, utilize the complexing action between metal ion and the polymine, polymine is adsorbed onto on the matrix resin surface, get intermediate product III;
4) chemically crosslinked of sorbent material.Being about to intermediate product III, to put into concentration be that 2%～50% linking agent polyaldehyde solution reacts, make to be adsorbed on the lip-deep polymine of matrix resin and to be cross-linked with each other, securely attached on the matrix resin, intermediate product IV:
5) soda acid wash-out typing.Promptly adopt acid solution with the metal ion wash-out among the intermediate product IV, with the alkaline solution typing, promptly get described resin then:.
The present invention can bring following beneficial effect: (1) raw material is conventional slightly acidic macroporous resin, and is cheap, and the source is abundant; (2) synthesis technique is simple, and building-up process is controlled easily, the combined coefficient height; (3) it has very high ligand complex ability, and kinetics of adsorption is good, and loading capacity is bigger, and selectivity is good, and wash-out is easy; (4) enriching and recovering of multiple precious metal, the purification that contains the trade effluent of heavy metal element or radioelement had application promise in clinical practice; (5) having alkaline amido palace can roll into a ball, in ambient air and industrial gaseous waste to HCl, SO
2, H
2The absorption cleaning aspect of sour gas such as S also has a wide range of applications.
Counterweight metals like gold of the present invention, copper, mercury, chromium, uranium, Thorium etc. have excellent absorption and select performance, can be used for the recovery of the above-mentioned heavy metal ion in the broad acidity scope medium and the purification of trade effluent, the enriching and recovering of heavy metal in the seawater contains the fields such as purification of the trade effluent of radioelement.
Embodiment
Example 1:
(1) the common commercially available D113 resin of weighing 8g is put into Erlenmeyer flask, and to the NaOH solution 200ml that wherein adds 30%, behind the vibration 3h, suction filtration cleans to neutral under normal temperature condition; (2) measuring 200ml concentration is 5% CuSO
4Solution adds in the Erlenmeyer flask, and normal temperature vibration 6h post-flush is clean; (3) measuring 200ml concentration is 2% polymine (molecular weight is 75000) solution, adds in the Erlenmeyer flask, and the normal temperature vibration was rinsed well after 12 hours; (4) measuring 150ml concentration is 5% glutaraldehyde solution, adds in the Erlenmeyer flask, and the normal temperature vibration was rinsed well after 12 hours; (5) use the H of 5N respectively
2SO
4The NH of solution and 2N
3H
2After the O washing makes the transition, to neutral, promptly make resin with distilled water flushing.
This resin is under 4.5 the condition, to Cu at PH
2+Saturated adsorption capacity can reach 0.84mmol (Cu)/g (doing).
Embodiment 2
(1) weighing 5g Amberlite XAD-7HP (polymethyl acrylate class polymeric adsorbent) puts into Erlenmeyer flask, and to the NaOH solution 200ml that wherein adds 20%, behind hydrolysis 3h under 65 ℃ of conditions, suction filtration cleans to neutral;
(2) measuring 200ml concentration is 7% CuSO
4Solution adds in the Erlenmeyer flask, and normal temperature vibration 6h post-flush is clean;
(3) measuring 200ml concentration is 5% polymine (molecular weight is 75000) solution, adds in the Erlenmeyer flask, and 12 hours post-flush of normal temperature vibration are clean;
(4) measuring 150ml concentration is 10% glutaraldehyde solution, adds in the Erlenmeyer flask normal temperature vibration 12 hours;
(5) use the H of 2N respectively
2SO
4The NH of solution and 2N
3H
2After the O washing made the transition, distilled water flushing was promptly made resin to neutral.
This resin is under 4.1 the condition, to UO at PH
4 2+Saturated adsorption capacity can reach 0.71mmol (U)/g (doing).
Embodiment 3
(1) weighing 5g Amberlite XAD-7HP (polymethyl acrylate class polymeric adsorbent) puts into Erlenmeyer flask, and to the NaOH solution 200ml that wherein adds 30%, behind hydrolysis 2h under 95 ℃ of conditions, suction filtration is clear to neutral;
(2) measuring 200ml concentration is 5% CuSO
4Solution adds Erlenmeyer flask, and normal temperature vibration 6h post-flush is clean;
(3) measuring 200ml concentration is 3% polymine (molecular weight is 20000) solution, adds Erlenmeyer flask, and normal temperature vibration 6h post-flush is clean;
(4) measuring 150ml concentration is that 5% glutaraldehyde is molten, adds Erlenmeyer flask, normal temperature vibration 12h.;
(5) use the H of 2N respectively
2SO
4The NH of solution and 2N
3H
2After the O washing made the transition, distilled water flushing promptly made novel chelate resin to neutral.
This resin is under 5 the condition, to Cd at PH
2+Saturated adsorption capacity can reach 1.06mmol (Cd)/g (doing).
Embodiment 4
With CuSO
45H
2O is made into Cu
2+Concentration is that 32ppm is standby with the aqueous solution 500ml of HC solution regulator solution PH about 3.7.In addition PEI (polymine) the resin 100mg that the present invention relates to is added in the above-mentioned solution of 20ml, vibration 24h leaches resin later under the room temperature, measures remaining Cu in the solution
2+Concentration is 0.42ppm, and resin is to Cu
2+Clean absorption rate reach 98.7%
Embodiment 5
With Cd (NO
3)
24H
2O is made into Cd
2+Concentration is 8.95ppm, and is standby with the aqueous solution 500ml of HC solution regulator solution PH about 3.7.In addition PEI (polymine) the resin 100mg that the present invention relates to is added in the above-mentioned solution of 20ml, vibration 24h leaches resin later under the room temperature, measures remaining Cd in the solution
2+Concentration is 0.32ppm, and resin is to Cd
2+Clean absorption rate reach 96.4%%.
Claims (9)
1, a kind of resin, it is characterized in that: this resin is to adopt the slightly acidic macroporous resin as carrier, heavy metal ion is gone up in its exchange, utilize the avidity between heavy metal ion and the water-soluble macromolecule metal ion adsorbent polymine again, polymine is adsorbed on the macroporous resin surface, and then makes it securely attached to making on the matrix resin by linking agent.
2, resin according to claim 1 is characterized in that: the molecular weight of described water-soluble macromolecule metal ion adsorbent polymine is 500-75000.
3, resin according to claim 1 is characterized in that: described macroporous resin carrier is a slightly acidic polystyrene type macroporous resin.
4, resin according to claim 1 is characterized in that: described macroporous resin carrier is a slightly acidic polymethyl acrylate class macroporous resin.
5, resin according to claim 1 is characterized in that: described macroporous resin carrier is a slightly acidic polymethylmethacrylate class macroporous resin.
6, resin according to claim 1 is characterized in that: described macroporous resin carrier is a slightly acidic polypropylene nitrile macroporous resin.
7, resin according to claim 1 is characterized in that: linking agent is oxalic dialdehyde or suceinic aldehyde or glutaraldehyde or its mixture.
8, a kind of synthetic method of making the described resin of claim 1 is characterized in that it has the following steps:
1) under 30-100 ℃ of condition, the macroporous resin carrier is put into the strong alkali aqueous solution that concentration is 4%-30%, makes it transform into the Na type, intermediate product I;
2) intermediate product I being put into concentration is that the heavy metallic salt solution of 1%-35% carries out ion exchange reaction, intermediate product II;
3) under the normal temperature, it is that 0.5%-50% polyethyleneimine: amine aqueous solution reacts that intermediate product II is put into concentration, gets intermediate product III;
4) under the normal temperature, it is that the polyaldehyde solution of 2%-50% reacts that intermediate product III is put into concentration, intermediate product IV;
5) adopt acid solution with the metal ion wash-out among the intermediate product IV, with the alkaline solution typing, promptly get described resin then.
9, synthetic method according to claim 8 is characterized in that: metal salt solution can be the salts solution of copper, lead, zinc, cadmium, mercury, gold, chromium, uranium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021290520A CN1188456C (en) | 2002-08-30 | 2002-08-30 | Chelate resin and its synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021290520A CN1188456C (en) | 2002-08-30 | 2002-08-30 | Chelate resin and its synthesis method |
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| Publication Number | Publication Date |
|---|---|
| CN1478807A CN1478807A (en) | 2004-03-03 |
| CN1188456C true CN1188456C (en) | 2005-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021290520A Expired - Lifetime CN1188456C (en) | 2002-08-30 | 2002-08-30 | Chelate resin and its synthesis method |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363374C (en) * | 2005-06-02 | 2008-01-23 | 江南大学 | Process for extracting maltitol from maltitol solution |
| CN100393410C (en) * | 2006-08-18 | 2008-06-11 | 南京大学 | Resin base adsorbent with high selectivity to heavy metal and preparing process thereof |
| CN101607191B (en) * | 2008-06-18 | 2011-08-24 | 上海博旭复合装饰材料有限公司 | Liner for separating metal ions and preparation method thereof |
| CN101869826B (en) * | 2010-06-13 | 2012-11-14 | 北京欧凯纳斯科技有限公司 | High-polymer compound chelated with heavy metal elements as well as preparation method and application thereof |
| CN102350318B (en) * | 2011-07-11 | 2015-02-04 | 邯郸派瑞电器有限公司 | Formaldehyde adsorption resin and preparation method thereof |
| CN102380351A (en) * | 2011-08-08 | 2012-03-21 | 邯郸派瑞电器有限公司 | Method for synthesizing formaldehyde adsorption resin |
| CN107973928A (en) * | 2017-12-30 | 2018-05-01 | 邯郸派瑞电器有限公司 | A kind of heavy metal chelate resin and preparation method thereof |
| CN109999761A (en) * | 2018-12-31 | 2019-07-12 | 邯郸派瑞电器有限公司 | A kind of polyethylene imine resin composite material, preparation method and application |
| CN115646467A (en) * | 2022-11-10 | 2023-01-31 | 厦门大学 | Heavy metal adsorbent based on modified waste flower mud and preparation method thereof |
-
2002
- 2002-08-30 CN CNB021290520A patent/CN1188456C/en not_active Expired - Lifetime
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