CN103172161A - Compound heavy metal chelating agent - Google Patents
Compound heavy metal chelating agent Download PDFInfo
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- CN103172161A CN103172161A CN2013100910233A CN201310091023A CN103172161A CN 103172161 A CN103172161 A CN 103172161A CN 2013100910233 A CN2013100910233 A CN 2013100910233A CN 201310091023 A CN201310091023 A CN 201310091023A CN 103172161 A CN103172161 A CN 103172161A
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- heavy metal
- triazine
- chelating agent
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Abstract
The invention discloses a compound heavy metal chelating agent which is prepared by carrying out reactions on water, a polyamine compound, halogenated alkylene oxide and 1,3,5-triazine-2,4,6- trithiol trisodium salt. A polyquaternary amine salt flocculant prepared by carrying out a chain-added crosslinking reaction on the halogenated alkylene oxide and the polyamine compound is effectively matched with the 1,3,5-triazine-2,4,6-trithiol trisodium salt to perform the cooperative action so as to remove heavy metal ions from wastewater. Therefore, the prepared heavy metal chelating agent maintains the advantages of TMT-15 being environment-friendly and strong in chelating ability, and overcomes the disadvantages of the TMT-15 being small in floccus body and difficult in precipitation filtering. During the subsequent process, by utilizing the compound heavy metal chelating agent, the heavy metal content in effluent is below the national standard under the condition that a polyacrylamide flocculant is not added additionally.
Description
Technical field
The present invention relates to a kind of technology of preparing of compound heavy metal chelant.
Background technology
In recent years, oneself becomes the problem that people pay special attention to contain the heavy metal ion Industrial Wastewater Treatment, these wastewater sources are various, mainly by mechanical workout, plating, mining, the smelting of iron and steel and non-ferrous metal and chemical enterprise produce, the kind of heavy metal ion, content and exist form to there are differences along with different production industries alter a great deal.Wherein electroplating wastewater becomes one of representative unmanageable trade effluent, mainly due to containing a large amount of heavy metal ion in waste water, directly enter not only contaminate environment of water body, also wasted a large amount of valuable metals, effective improvement of electroplating wastewater causes extensive attention at home and abroad.
Although developed now the method for harmful heavy metal ion in multiple removal water, as absorption method, ion exchange method, reverse osmosis method, biological process etc., effect is better, lower-cost process for treating heavy-metal waste water but the chelating precipitator method are still, principle is that the sequestrant of sulfur-bearing, nitrogen functional group can form water-fast stable comple with heavy metal ion, these Stability constant of complexes are very high, thereby most heavy metal ion are separated from water, reached the purpose that purifies water.In order to make sequestrant have flocculating property preferably, usually use the high-molecular chelating agent of certain degree of crosslinking.
Heavy metal chelating agent commonly used is mainly the derivative of dithiocarbamic acid compounds at present, as polyamines dithio formate, polyethylene imine based xanthogenic acid, polyamines-epihalohydrin copolymer xanthogenate, polyacrylamide xanthogenate etc.More bibliographical information the has been arranged synthetic and effect of this class heavy metal chelating agent, for example publication number is the synthetic and application in heavy metal wastewater thereby that " a kind of synthetic method of dithioamino formic acid and diivinyl triamineethyl polymers " of CN1831020A discloses a kind of crosslinked polymer dithiocar-bamate.Publication number be CN101173019A's " a kind of polyvinyl alcohol is the synthetic method of the high-molecular chelating agent of basic chain " disclose and a kind ofly had than high-crosslinking-degree and effectively synthetic method and the application example of the high-molecular chelating agent of group.But in actual applications, there is following shortcoming in this class heavy metal chelating agent: the one, have toxicity, and organism in water is had lethal.The 2nd, due to reasons such as chelation group part vacancies, need to use the heavy metal chelating agent of excessive several times just can make the heavy metals ion up to standard, cause the waste water after processing to contain certain density heavy metal chelating agent, environment is caused damage, and it is partially yellow to use the water colour pool.
On the other hand, 1.3.5-triazine-2.4.6-three mercaptan trisodium salts (TMT-15) are nonpoisonous and tasteless, be called as environmentally friendly product, situation about especially heavy metal being existed with complexing salt form (EDTA, citric acid etc.), also can bring into play good removal effect, thereby be widely used in heavy metal ion-containing waste water processing industry.This heavy metal chelating agent is micromolecular compound, though sequestering power is strong, but little with the flco that forms after complexing of metal ion, settling property is poor, suspend in water for a long time and be difficult for precipitation, need follow-up excessive coagulant aids polyacrylamide and the coagulating agent (Polyferric Sulfate, poly-aluminium) of adding, waste time and energy, usually because precipitation does not totally make the water outlet heavy metals exceeding standard.
Summary of the invention
Technical problem to be solved by this invention just is to provide a kind of compound heavy metal chelant that is applied to contain the heavy metal ion Industrial Wastewater Treatment, and is more friendly and make wastewater treatment process more convenient to environment.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of compound heavy metal chelant is characterized in that: this compound heavy metal chelant is made by water, polyamine compounds, haloalkylene oxide and 1.3.5-triazine-2.4.6-three mercaptan trisodium salt reactions.
Preferably, described polyamine compounds is a kind of or its mixture in quadrol, diethylenetriamine, triethylene tetramine, polyethylene polyamine or polyethylene polyamines.
Preferably, described haloalkylene oxide is epoxy chloropropane, and the addition of described epoxy chloropropane is 1/10～1/2 of polyamine compounds with molar ratio computing.
Preferably, the addition of described epoxy chloropropane is 1/6～1/3 of polyamine compounds with molar ratio computing.
Preferably, described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts add with the form of solid or the aqueous solution, and addition is 0.1～2.0 times of polyamine compounds with molar ratio computing.
Preferably, the addition of described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts is 0.4～1.6 times of polyamine compounds with molar ratio computing.
The polyquaternary amine salt flocculation agent that the present invention uses haloalkylene oxide and polyamine compounds to carry out the preparation of chain crosslinking reaction effectively coordinates with 1.3.5-triazine-2.4.6-three mercaptan trisodium salts, and the effect of heavy metals ion is removed in collaborative performance.Thereby the heavy metal chelant of the present invention's preparation has kept the TMT-15 environmental friendliness, the advantage that sequestering power is strong, overcome again its flco little, the shortcoming of the sad filter of precipitation can be in the situation that follow-uply need not separately to add polyacrylamide flocculant and make the water outlet heavy metal content lower than national standard.
Embodiment
The preparation method of the compound heavy metal chelant of the present invention comprises the steps:
1) add entry and polyamine compounds and stir in reactor;
2) slowly drip haloalkylene oxide and keep temperature to be no more than 50 ℃ in reactor;
3) reactor is warming up between 50～90 ℃, and continues stirring reaction 2～6 hours at this temperature;
4) logical water coolant is down to 25～35 ℃ in reactor, then adds 1.3.5-triazine-2.4.6-three mercaptan trisodium salts, stirs and namely gets compound heavy metal chelant in 0.5～1 hour.
Wherein, described polyamine compounds is a kind of or its mixture in quadrol, diethylenetriamine, triethylene tetramine, polyethylene polyamine or polyethylene polyamines.Described haloalkylene oxide is epoxy chloropropane, and the addition of described epoxy chloropropane is 1/10～1/2 of polyamine compounds with molar ratio computing, is preferably 1/6～1/3.Described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts add with the form of solid or the aqueous solution, described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts (TMT-Na3) can be bought by market and obtain, can be also synthetic the obtaining of the disclosed method of CN101591303A " for the preparation of the method for the trisodium salt of 2.4.6-tri-thiol s-triazine " by publication number, the addition of described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts is 0.1～2.0 times of polyamine compounds with molar ratio computing in addition, is preferably 0.4～1.6 times.
Further illustrate the present invention below in conjunction with specific embodiment, but the present invention should not be subject to following embodiment.
Embodiment 1
Add 1 premium on currency in reactor, turn on agitator adds 41 gram quadrols, slowly drips epoxy chloropropane 63 grams, keeps temperature to be no more than 50 ℃ in the dropping process.Be warmed up to 70 ℃ of stirring reactions 2 hours after dripping off.Then cool to 25 ℃, add 1.3.5-triazine-2.4.6-three mercaptan trisodium salt 82 grams, stirring obtains achromaticity and clarification liquid after half an hour and is heavy metal chelant.
Embodiment 2
Add 1 premium on currency in reactor, turn on agitator adds 70 gram diethylenetriamines, slowly drips epoxy chloropropane 32 grams, keeps temperature to be no more than 50 ℃ in the dropping process.Be warmed up to 85 ℃ of stirring reactions 2 hours after dripping off.Then cool to 25 ℃, add 1.3.5-triazine-2.4.6-three mercaptan trisodium salt 82 grams, stirring obtains achromaticity and clarification liquid after half an hour.
Embodiment 3
Add 1 premium on currency in reactor, turn on agitator adds 95 gram triethylene tetramines, slowly drips epoxy chloropropane 90 grams, keeps temperature to be no more than 50 ℃ in the dropping process.Be warmed up to 85 ℃ of stirring reactions 2 hours after dripping off.Then cool to 25 ℃, add 1.3.5-triazine-2.4.6-three mercaptan trisodium salt 82 grams, stirring obtains achromaticity and clarification liquid after half an hour.
Embodiment 4
Add 1 premium on currency in reactor, turn on agitator adds 70 gram diethylenetriamines, slowly drips epoxy chloropropane 68 grams, keeps temperature to be no more than 50 ℃ in the dropping process.Be warmed up to 90 ℃ of stirring reactions 2 hours after dripping off.Then cool to 25 ℃, add 1.3.5-triazine-2.4.6-three mercaptan trisodium salt 82 grams, stirring obtains achromaticity and clarification liquid after half an hour.
Embodiment 5
Add 1 premium on currency in reactor, turn on agitator adds 70 gram diethylenetriamines, slowly drip epoxy chloropropane 32 grams, keep temperature to be no more than 50 ℃ in the dropping process, then dripped 106 gram dithiocarbonic anhydride in 1 hour, be warmed up to 85 ℃ of stirring reactions 2 hours after dripping off.Then cool to 25 ℃, add 1.3.5-triazine-2.4.6-three mercaptan trisodium salt 82 grams, stirring obtains orange liquid after half an hour.
Embodiment 6
Above-mentioned products obtained therefrom is carried out heavy metal remove experiment test, test procedure is as follows: the simulated wastewater of first preparing copper ions 53.1mg/L and nickel ion 46.4mg/L.Delivery is intended waste water 1L, adds the heavy metal chelant 0.7mL by above-mentioned example preparation, stirs after 10 minutes standing 15 minutes, filters the throw out of generation, then uses the heavy metal content of spectrophotometry waste water remnants.The results are shown in Table one.
Table one heavy metal is removed test result
Presentation of results can keep very high removal of heavy metal ions rate in the situation that the heavy metal chelant consumption is very low.
Embodiment 7
Get the waste water with the identical heavy metal concentration of upper example, the sample that embodiment 3 is made and commercially available TMT-15 product performance compare.Embodiment 3 the same examples of sample test method, commercially available TMT-15 product stirred 10 minutes, added a little anion-polyacrylamide, then stirred after 15 minutes standing 15 minutes, then filter the throw out that generates, use at last the heavy metal content of spectrophotometry waste water remnants.The results are shown in Table two.
Table two the present invention and the contrast of commercially available TMT-15 product performance
Result shows with respect to commercially available TMT-15 product, and product of the present invention is used for the heavy metals ion remaval better effect.
Claims (6)
1. compound heavy metal chelant is characterized in that: this compound heavy metal chelant is made by water, polyamine compounds, haloalkylene oxide and 1.3.5-triazine-2.4.6-three mercaptan trisodium salts reactions.
2. a kind of compound heavy metal chelant according to claim 1, it is characterized in that: described polyamine compounds is a kind of or its mixture in quadrol, diethylenetriamine, triethylene tetramine, polyethylene polyamine or polyethylene polyamines.
3. a kind of compound heavy metal chelant according to claim 1, it is characterized in that: described haloalkylene oxide is epoxy chloropropane, the addition of described epoxy chloropropane is 1/10～1/2 of polyamine compounds with molar ratio computing.
4. a kind of compound heavy metal chelant according to claim 3, it is characterized in that: the addition of described epoxy chloropropane is 1/6～1/3 of polyamine compounds with molar ratio computing.
5. a kind of compound heavy metal chelant according to claim 1, it is characterized in that: described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts add with the form of solid or the aqueous solution, and addition is 0.1～2.0 times of polyamine compounds with molar ratio computing.
6. a kind of compound heavy metal chelant according to claim 5, it is characterized in that: the addition of described 1.3.5-triazine-2.4.6-three mercaptan trisodium salts is 0.4～1.6 times of polyamine compounds with molar ratio computing.
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| CN201310091023.3A CN103172161B (en) | 2013-03-21 | 2013-03-21 | Compound heavy metal chelating agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104531159A (en) * | 2014-12-09 | 2015-04-22 | 成都新朝阳作物科学有限公司 | Soil repairing agent and preparation method thereof |
| CN104941590A (en) * | 2014-03-31 | 2015-09-30 | 华东理工大学 | Material for detecting and separating metal ion in aqueous solution and preparation method of material |
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| CN101700922A (en) * | 2009-11-20 | 2010-05-05 | 大连理工大学 | cationic starch flocculant |
| CN101863544A (en) * | 2010-06-29 | 2010-10-20 | 湖南科技大学 | Cyanuric acid-based heavy metal chelating flocculant and preparation method thereof |
| KR20110034112A (en) * | 2009-09-28 | 2011-04-05 | 영창케미칼 주식회사 | Reclaiming process of coolant and reclaimed coolant |
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- 2013-03-21 CN CN201310091023.3A patent/CN103172161B/en not_active Expired - Fee Related
Patent Citations (3)
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| KR20110034112A (en) * | 2009-09-28 | 2011-04-05 | 영창케미칼 주식회사 | Reclaiming process of coolant and reclaimed coolant |
| CN101700922A (en) * | 2009-11-20 | 2010-05-05 | 大连理工大学 | cationic starch flocculant |
| CN101863544A (en) * | 2010-06-29 | 2010-10-20 | 湖南科技大学 | Cyanuric acid-based heavy metal chelating flocculant and preparation method thereof |
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| MATTHEW M. MATLOCK等: "Aqueous leaching properties and environmental implications of cadmium, lead and zinc Trimercaptotriazine (TMT) compounds", 《WATER RESEARCH》 * |
| 修莎 等: "重金属捕集剂XL9对含铜电镀废水处理效果的研究", 《环境工程学报》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941590A (en) * | 2014-03-31 | 2015-09-30 | 华东理工大学 | Material for detecting and separating metal ion in aqueous solution and preparation method of material |
| CN104941590B (en) * | 2014-03-31 | 2019-08-13 | 华东理工大学 | A kind of material and preparation method thereof for detecting with separating metal ion in aqueous solution |
| CN104531159A (en) * | 2014-12-09 | 2015-04-22 | 成都新朝阳作物科学有限公司 | Soil repairing agent and preparation method thereof |
| CN104531159B (en) * | 2014-12-09 | 2018-02-16 | 成都新朝阳作物科学有限公司 | Soil-repairing agent and preparation method thereof |
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