CN100441611C - Heavy metal chelate resin containing xanthogen and carbonyl and its preparation and uses - Google Patents
Heavy metal chelate resin containing xanthogen and carbonyl and its preparation and uses Download PDFInfo
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- CN100441611C CN100441611C CNB2006100429436A CN200610042943A CN100441611C CN 100441611 C CN100441611 C CN 100441611C CN B2006100429436 A CNB2006100429436 A CN B2006100429436A CN 200610042943 A CN200610042943 A CN 200610042943A CN 100441611 C CN100441611 C CN 100441611C
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Abstract
The present invention provides a heavy metal chelating resin which is synthesized by two steps: (1) the synthesis of dixanthogen salts: first, a certain amount of potassium hydroxide is dissolved in water, and 30% to 32% water solution is formed. Then, the potassium hydroxide solution is cooled to 4 DEG to 6 DEG C, diol of which the weight is 0.5 to 1.7 times of that of the potassium hydroxide is added into the potassium hydroxide solution, and the diol reacts with the potassium hydroxide for 25 to 35 minutes. The mixture continues to be cooled to 1 to 3 DEG C, then carbon bisulfide of which the weight is 1.4 to 1.6 times of that of the potassium hydroxide is added, and reaction is carried out for 3 to 5 hours in a stirring mode at room temperature. Dixanthogen potassium salt is obtained through reduced pressure distillation, filtration, washing with isopropanol and drying; (2) resin synthesis: dixanthogen potassium salts are fully dissolved in N, N-dimethylformamide solvents, and N, N-dimethylformamide solution is added into the mixture in a stirring mode at room temperature, wherein terephthaloyl chloride of which the weight is 0.5 to 0.8 time of that of the dixanthogen potassium salts is dissolved in the N, N-dimethylformamide solution. The mixture is continuously stirred for 3 to 4 hours, water is added into the mixture, suction filtration is carried out to the mixture, and the filtered mixture is washed with distilled water and acetone and dried, so that the heavy metal chelating resin is obtained. The chelating resin has strong chelating capacity for heavy metal ions, so the chelating resin is applied to the treatment of heavy metal wastewater.
Description
Technical field
The invention belongs to sewage treatment area, relate to the heavy metal chelant in a kind of heavy metal containing wastewater treatment.Relate in particular to a kind of heavy metal chelate resin and application in the heavy metal water treatment thereof that contains xanthogen and contain the xanthogen hydroxyl.
Background technology
Along with the fast development of national economy and industry, the pollution of environment is serious day by day, and the processing of waste water has in recent years caused people's attention.The important source of pollution of contaminate environment water quality are the heavy metal ion in the trade effluent.Heavy metal wastewater thereby mainly drenches the waste water of industry such as immersion, mill tailings draining, non-ferrous metals smelting works' dedusting draining, Non-ferrous Metals Processing Factory's acid washing water, Electroplate Factory's plating piece washing water, Steel Plant's pickling draining and electrolysis, agricultural chemicals, medicine, paint, pigment from mine drainage, waste rock pile.Though the heavy metal indispensable metallic element that is HUMAN HEALTH extensively is present in the muscle and bone of human body, content seldom, if excess will produce great harm to human body.The method of handling heavy metal wastewater thereby mainly contains Coagulation Method, oxidation reduction process, electrolytic process, air supporting method, neutralization precipitation method, absorption method, ion exchange method, solvent extration, membrane separation process, biological treatment etc.And macromolecular heavy metal chelating agent has advantages such as cost is low, effect stability to the processing of heavy metal wastewater thereby, wherein use the sulfur-bearing resin more to the report that metal ion adsorbs, its reason is the cross-linked polymer that resin is generally indissoluble, is easy to and liquid phase separation; And sulfurous organic compound has the character of soft base or middle alkali, and metal ion belongs to soft acid more, and both easily form stable chelate.
Domestic and international useful insoluble starch xanthate is made trapping agent processing heavy metal ion-containing waste water and has been received good effect, but starch xanthate easily decomposes and difficult regeneration, and its application is restricted.
Summary of the invention
The purpose of this invention is to provide and a kind of metal ion is had heavy metal chelate resin good absorption property, that contain xanthogen; A kind of preparation technology of this heavy metal chelate resin also is provided simultaneously;
Another object of the present invention provides the application of above-mentioned resin in heavy metal containing wastewater treatment.
The present invention contains the heavy metal chelate resin of xanthogen, is to be formed by following prepared:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 30%～32% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the glycol of 0.5～1.7 times of weight of potassium hydroxide, reacted 25～35 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.4～1.6 times of weight of potassium hydroxide then, under agitation be warming up to room temperature, reacted 3～5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get;
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.5～0.8 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 3～4 hours, add water, suction filtration, with distilled water and washing with acetone, dry coal, promptly get the heavy metal chelate resin that the present invention contains xanthogen.
In the 1. two xanthogenate of described step synthetic, in solution, add dithiocarbonic anhydride after, can be earlier 5～10 ℃ of stirring reactions of temperature 0.5～1.5 hour, be warming up to room temperature then, continue reaction 3～5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get.
The glycol that the present invention adopts is ethylene glycol or glycol ether or Triethylene glycol or tetraethylene-glycol.
The characteristics of heavy metal chelate resin of the present invention:
1, the heavy metal chelate resin of the present invention's preparation contains xanthogen and carbonyl simultaneously, and metal ion is had stronger coordination, can form stable chelate with metal ion; And contain hydrophilic macromolecular scaffold, can obviously accelerate rate of adsorption.After measured, the heavy metal chelate resin of the present invention's preparation can reach 90% to the adsorption rate of heavy metal ion;
2, the heavy metal chelate resin of the present invention's preparation is water insoluble, is easy to separate when using;
3, the heavy metal chelate resin of the present invention's preparation is suitable for using under slightly acidic condition, can use in wide temperature range, requires lower to ambient temperature conditions;
4, preparation technology of the present invention is simple, easy handling, and cost is low, is convenient to industrialization.
Because above-mentioned characteristic of the present invention can be used for the heavy metal water technology.
The method that heavy metal chelate resin of the present invention is handled heavy metal wastewater thereby is: the resin of heavy metal wastewater thereby weight 0.8%～1.1% is placed heavy metal wastewater thereby, and at room temperature stirring reaction got final product in 10～60 minutes.
Below with Ni
2+Be example, the influence of five aspects of consumption, pH value, time, temperature, loading capacity of resin to absorption property is described by experiment.
1, the influence of resin demand
Get the certain density heavy metal solution of 100ml, add the resin SCX of different amounts, at room temperature stirring reaction is 30 minutes, carries out suction filtration with the middling speed quantitative paper, and filtrate is carried out ion detection; Survivor ion concentration in the determined by ultraviolet spectrophotometry filtrate; Minusing calculates adsorption rate.Wherein resin 1, resin 2, resin 3, resin 4 are respectively to be the chela and the resin of glycol preparation with glycol ether, Triethylene glycol, tetraethylene-glycol.Resin demand sees Table 1 and Fig. 1 to the adsorption of metal ions Effect on Performance.
Table 1 resin demand is to the adsorption of metal ions Effect on Performance
As shown in Table 1, along with the increase of resin demand, the residual metal ionic concn reduces, and adsorption rate increases thereupon, but reaches 0.20g when above when resin demand, underspeeds and obviously slows down, and the while adsorption rate tends towards stability.
2, the influence of pH value
Get the certain density heavy metal solution of 100ml, regulate different pH with buffered soln, add the SCX of 0.1g, at room temperature stirring reaction is 30 minutes, carries out suction filtration with the middling speed quantitative paper, and filtrate is carried out ion detection; Survivor ion concentration in the determined by ultraviolet spectrophotometry filtrate; Minusing calculates adsorption rate.Wherein resin 1, resin 2, resin 3, resin 4 are respectively to be the chela and the resin of glycol preparation with glycol ether, Triethylene glycol, tetraethylene-glycol.The pH value sees Table 2 and Fig. 2 to the adsorption of metal ions Effect on Performance.
Table 2 pH value is to the adsorption of metal ions Effect on Performance
As shown in Table 2, the pH value is bigger to plastic resin treatment metallic wastewater influence, is that 4 o'clock treatment effects are general at pH, but along with the continuous increase of pH value, processing power obviously strengthens.When pH was 6～7, adsorption rate reached maximum value, and sulphur atom is difficult for losing coordination ability in the resin under acidic conditions.When pH is 8 when above, processing power begins to descend on the contrary, and this may be because metal ion at this pH value range content hydrolysis takes place easily, is unfavorable for adsorbing; And resin is unstable under alkaline condition, easily decomposes.So this resin should use under slightly acidic condition.
3, the influence in reaction times
Get the certain density heavy metal solution of 300ml, add the SCX of 1g, at room temperature electronic stirring reaction different time, carry out suction filtration with the middling speed quantitative paper, filtrate is carried out ion detection, the survivor ion concentration in the determined by ultraviolet spectrophotometry filtrate, minusing calculates adsorption rate.Reaction times sees Table 3 and Fig. 3 to the adsorption of metal ions Effect on Performance.
Table 3 reaction times is to the adsorption of metal ions Effect on Performance
As shown in Table 3, resin and Ni
2+Reaction rapider, reaction has reached big adsorption rate when proceeding to 30min, after reaction proceeded to 40min, adsorption rate tended towards stability, this is because Ni
2+Density loss, intermolecular effective collision reduces, and speed of response descends to some extent, and resin becomes stable to the adsorption rate of metal ion simultaneously.
4, the influence of temperature of reaction
Get the certain density heavy metal solution of 100ml, add the SCX of 0.1g, stirring reaction is 30 minutes under differing temps, carry out suction filtration with the middling speed quantitative paper, filtrate is carried out ion detection, the survivor ion concentration in the determined by ultraviolet spectrophotometry filtrate, minusing calculates adsorption rate.Temperature of reaction sees Table 4 and shown in Figure 4 to the adsorption of metal ions Effect on Performance.
Table 4 temperature of reaction is to the adsorption of metal ions Effect on Performance
As can be seen from Table 4, temperature of reaction is less to the influence of adsorption rate, so such resin can use in wide temperature range, requires lower to ambient temperature conditions.
5, loading capacity experiment
Get the heavy metal solution of 100ml different concns, add a certain amount of SCX, at room temperature the stirring reaction certain hour, carry out suction filtration with the middling speed quantitative paper, filtrate is carried out ion detection, the survivor ion concentration in the determined by ultraviolet spectrophotometry filtrate, minusing calculates adsorption rate.Concentration of heavy metal ion sees Table 5 and Fig. 5 to the resin absorption Effect on Performance.
Table 5 strength of solution is to the adsorption of metal ions Effect on Performance
As shown in Table 5, the absorption property of resin is directly related with nickel concentration in the solution.The adsorption rate of resin increases with the increase of metal ion starting point concentration, and in the concentration range of being measured, the loading capacity of resin increased along with the increase of nickel ion concentration before this, when nickel ion concentration reaches 109mgL
-1After, the adsorptive power of resin is tending towards saturated, and it is slow that the increase of loading capacity is tending towards.
The present invention compared with prior art has the following advantages:
1, the present invention's preparation contains the method for the resin of xanthogen and carbonyl simultaneously, and is simple to operate, not high to environmental requirement.
2, four kinds of resin products of the present invention's preparation are water insoluble, are easy to separate when using.
3, the resin product of the present invention's preparation is suitable for using under slightly acidic condition, can use in wide temperature range, requires lower to ambient temperature conditions.
4, the resin product of the present invention's preparation has stronger coordination to metal ion, can form stable chelate with metal ion; And contain the hydrophilic macromolecule skeleton, can obviously accelerate rate of adsorption.
Description of drawings
Fig. 1 is that resin demand is to the adsorption of metal ions Effect on Performance
Fig. 2 pH value is to the adsorption of metal ions Effect on Performance
Fig. 3 reaction times is to the adsorption of metal ions Effect on Performance
Fig. 4 temperature of reaction is to the adsorption of metal ions Effect on Performance
Fig. 5 strength of solution is to the adsorption of metal ions Effect on Performance
Embodiment
The preparation of embodiment 1, a kind of heavy metal chelate resin 1 comprises following two processing steps:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 30% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the ethylene glycol of 0.5 times of weight of potassium hydroxide, reacted 35 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.6 times of weight of potassium hydroxide then, under agitation be warming up to room temperature, reacted 5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get;
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.5 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 4 hours, add water, suction filtration, with distilled water and washing with acetone, drying, promptly get the heavy metal chelate resin that the present invention contains xanthogen.
The preparation of embodiment 2, a kind of heavy metal chelate resin 2 comprises following two processing steps:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 31% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the ethylene glycol glycol ether of 1.2 times of weight of potassium hydroxide, reacted 30 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.5 times of weight of potassium hydroxide then, earlier, be warming up to room temperature then, continue reaction 3 hours 5～10 ℃ of stirring reactions of temperature 0.5 hour; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get.
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.6 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 4 hours, add water, suction filtration, with distilled water and washing with acetone, drying, promptly get the heavy metal chelate resin that the present invention contains xanthogen.
The preparation of embodiment 3, a kind of heavy metal chelate resin 3 comprises following two processing steps:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 32% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the ethylene glycol Triethylene glycol of 1.5 times of weight of potassium hydroxide, reacted 35 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.4 times of weight of potassium hydroxide then, earlier, be warming up to room temperature then, continue reaction 4 hours 5～10 ℃ of stirring reactions of temperature 1 hour; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get.
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.7 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 3 hours, add water, suction filtration, with distilled water and washing with acetone, drying, promptly get the heavy metal chelate resin that the present invention contains xanthogen.
The preparation of embodiment 4, a kind of heavy metal chelate resin 4 comprises following two processing steps:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 30% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the ethylene glycol tetraethylene-glycol of 1.7 times of weight of potassium hydroxide, reacted 25 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.5 times of weight of potassium hydroxide then, earlier, be warming up to room temperature then, continue reaction 5 hours 5～10 ℃ of stirring reactions of temperature 1.5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get.
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.8 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 3.5 hours, add water, suction filtration, with distilled water and washing with acetone, drying, promptly get the heavy metal chelate resin that the present invention contains xanthogen.
The method that embodiment 5, resin of the present invention 1,2,3,4 are handled heavy metal wastewater thereby is: the resin of heavy metal wastewater thereby weight 0.8%～1.1% is placed heavy metal wastewater thereby, and at room temperature stirring reaction got final product in 10～60 minutes.
Claims (3)
1, a kind of heavy metal chelate resin that contains xanthogen and hydroxyl is to be formed by following prepared:
1. two xanthogenate is synthetic: earlier that a certain amount of potassium hydroxide is soluble in water, formation concentration is 30%～32% the aqueous solution; Potassium hydroxide solution is cooled to 4～6 ℃ again, adds the glycol of 0.5～1.7 times of weight of potassium hydroxide, reacted 25～35 minutes; Continue to be cooled to 1～3 ℃, add the dithiocarbonic anhydride of 1.4～1.6 times of weight of potassium hydroxide then, under agitation be warming up to room temperature, reacted 3～5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get;
2. resin is synthetic: two xanthogenic acid sylvite fully are dissolved in N, in the dinethylformamide solvent, the N that under stirring at room, adds the phthalyl chloride that is dissolved with two 0.5～0.8 times of weight of xanthogenic acid sylvite, dinethylformamide solution, continue to stir 3～4 hours, add water, suction filtration, with distilled water and washing with acetone, drying, promptly.
2, the heavy metal chelate resin that contains xanthogen and hydroxyl according to claim 1, it is characterized in that: in the 1. two xanthogenate of described step synthetic, after in solution, adding dithiocarbonic anhydride, earlier 5～10 ℃ of stirring reactions of temperature 0.5～1.5 hour, be warming up to room temperature then, continue reaction 3～5 hours; Underpressure distillation is filtered, and is used washed with isopropyl alcohol, the dry pair xanthogenic acid sylvite that get.
3, contain the heavy metal chelate resin of xanthogen and hydroxyl as claimed in claim 1 or 2, it is characterized in that: described glycol is ethylene glycol or glycol ether or Triethylene glycol or tetraethylene-glycol.
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| CNB2006100429436A CN100441611C (en) | 2006-06-05 | 2006-06-05 | Heavy metal chelate resin containing xanthogen and carbonyl and its preparation and uses |
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| CNB2006100429436A CN100441611C (en) | 2006-06-05 | 2006-06-05 | Heavy metal chelate resin containing xanthogen and carbonyl and its preparation and uses |
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| CN100441611C true CN100441611C (en) | 2008-12-10 |
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| RU2460694C1 (en) * | 2011-04-13 | 2012-09-10 | Государственное образовательное учреждение высшего профессионального образования "Уфимский государственный нефтяной технический университет" | Method of purifying waste water from cobalt, manganese and bromine |
| CN104556332A (en) * | 2014-12-25 | 2015-04-29 | 上海源育节能环保科技有限公司 | Heavy metal ion trapping agent and manufacturing method thereof |
| CN109772277A (en) * | 2019-03-19 | 2019-05-21 | 济南大学 | Adsorbents for lead ion pyrolytic and preparation method thereof in a kind for the treatment of of acidic wastewater |
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| CN85102714A (en) * | 1985-04-07 | 1986-03-10 | 国营惠丰机械厂 | Handle the serous cellulose xanthate method of electroplating wastewater |
| CN86108746A (en) * | 1986-12-26 | 1988-07-27 | 北京有色金属研究总院 | The glue of heavy metal ion removes agent and preparation method in the aqueous solution |
| CN1389502A (en) * | 2002-07-24 | 2003-01-08 | 山东美林亚生物科技有限公司 | Heavy metal chelant composite containing chitosan derivative |
-
2006
- 2006-06-05 CN CNB2006100429436A patent/CN100441611C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102714A (en) * | 1985-04-07 | 1986-03-10 | 国营惠丰机械厂 | Handle the serous cellulose xanthate method of electroplating wastewater |
| CN86108746A (en) * | 1986-12-26 | 1988-07-27 | 北京有色金属研究总院 | The glue of heavy metal ion removes agent and preparation method in the aqueous solution |
| CN1389502A (en) * | 2002-07-24 | 2003-01-08 | 山东美林亚生物科技有限公司 | Heavy metal chelant composite containing chitosan derivative |
Non-Patent Citations (4)
| Title |
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| 淀粉基黄原酸盐合成新工艺及其在废水处理中的应用. 龚盛昭.化工环保，第21卷第2期. 2001 |
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| 纤维素黄原酸酯对金属废水的处理试验. 金文刚.云南环境科学，第14卷第4期. 1995 |
| 纤维素黄原酸酯对金属废水的处理试验. 金文刚.云南环境科学，第14卷第4期. 1995 * |
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