CN102603046B - Heavy metal ion complexing agent, preparation method and applications thereof - Google Patents
Heavy metal ion complexing agent, preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses a heavy metal ion complexing agent, a preparation method and applications of the heavy metal ion complexing agent. The heavy metal ion complexing agent comprises the following components by weight: 4%-22% of polyamine, 10%-25% of alkali, 2%-10% of chloralkane, 28%-35% of CS2 (carbon disulfide) and 0-5% of alcohol. The heavy metal ion complexing agent can be prepared by conventional, simple and convenient operation, and can remove heavy metal ions in wastewater through the action of complexation, absorption, flocculation, precipitation and the like after being added into the wastewater, and the removal efficiency to heavy metal ion such as Pb, Cd, Ni, Hg and the like is more than or equal to 99%. According to the invention, the raw materials are wide in source, the preparation process is simple, the reaction condition is mild, the pollutant removal efficiency is high, new devices and new structures do not need to be arranged additionally in the practical application, the heavy metal ion complexing agent can be applied by only utilizing an existing preparing and adding system for water treatment agent, the application is simple, the application range is wide, the adaptability is strong, and the heavy metal ion complexing agent has the advantages of economy, high efficiency, safety, environmental protection and the like.
Description
Technical field
The invention belongs to waste water heavy metal contamination control techniques field, be specifically related to a kind of heavy metal ion complexing agent and its preparation method and application.
Background technology
2010, national industrial wastewater discharge total amount reached 237.5 hundred million tons, and wherein the heavy metal wastewater thereby quantity discharged is just above 4,000,000,000 tons.So the discharging of plurality of heavy metal waste water makes China's heavy metal pollution of water body problem become increasingly conspicuous, and according to incompletely statistics, the heavy metal contamination rate of China's river,lake and reservior substrate is up to 80.1%.Heavy metal mainly refers to Hg, Cd, Pb, Cr, As, Cu and Ni etc., mainly from industrial production such as chemical industry, non-ferrous metal selecting and purchasing and smelting, battery manufacturing, plating, printing and dyeing, pottery, plastics, because heavy metal has high toxicity, difficult degradation, characteristics such as easy enrichment, directly enter in the water body if the heavy metal that contains ionic state, complex state of above-mentioned industrial production and discharging is not treated, the not only hydrobiological existence of serious harm, also can be by the health of food chain enrichment and then harm humans, the havoc ecosystem causes serious economy loss.Therefore heavy metal pollution of water body becomes the significant problem that restriction China economy, social development and the people's livelihood are improved gradually, presses for and controls and administer.
At present, the treatment process of heavy metal wastewater thereby is more, normal adopt ion exchange method, electrolytic process, chemical precipitation method, the chelating precipitator method etc. are arranged.Wherein the ion exchange method treatment effect is good, but expensive.The treatment effect of electrolytic process is relatively poor, but also has the secondary pollution problem.Chemical precipitation method is at present domestic and international the most frequently used method, wherein adopt alkali neutralization precipitation method mostly, but this method is to containing the wastewater treatment complex procedures of various heavy, both sexes heavy metal, can't directly handle the heavy metal wastewater thereby that contains complexing agent, handle the pH value severe overweight that a large amount of alkali causes processed waste water that often need add up to standard, can produce a large amount of unsettled heavy metal hydroxide mud etc. in addition, have the secondary pollution problem.The chelating precipitator method are better, the lower-cost process for treating heavy-metal waste water of effect, and heavy metal complexometry development in recent years is very fast, have begun to use research and the existing practical application that the high molecular heavy metals ionic complexing agent is handled heavy metal wastewater thereby both at home and abroad.The key of the chelating precipitator method is to develop the heavy metal complexing flocculation agent of efficient and cheap, the more heavy metal ion complexing agent of research mostly contains dithiocarbamate-based functional group both at home and abroad at present, mainly can be divided into polymeric complexing agent and small molecules complexing agent two classes.The polymeric complexing agent molecular weight is big, and settling property is good, also has certain throwing out simultaneously, but its functional group's utilization ratio reduction, treatment effect is relatively poor, and along with the solubility property of increase polymeric complexing agent in water of molecular weight reduces; And functional group's utilization ratio height of small molecules complexing agent, but the throw out flco that generates is tiny, and settling property is bad, needs to add the flocculation medicament, just can make flco that comparatively ideal settling property is arranged; In addition, restricting an important factor of heavy metal ion complexing agent widespread use at present, is that the production cost of complexing agent is higher, makes processing cost higher, and application is restricted.
Therefore, for the control heavy metal wastewater thereby of economical and efficient pollutes, be necessary low in a kind of use cost of the basis of existing heavy metal ion complexing agent exploitation, contaminant removal efficiency is high and the novel heavy metal ion complexing agent of safety and environmental protection.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention provide a kind ofly not only had that small molecules complexing agent solubility property is good, functional group's utilization ratio height but also heavy metal ion complexing agent with advantages such as the polymeric complexing agent flco are big, settling property is good.
Another object of the present invention is to provide the preparation method of described heavy metal ion complexing agent.
A further object of the present invention is to provide the application of described heavy metal ion complexing agent.
The object of the invention is achieved through the following technical solutions:
A kind of heavy metal ion complexing agent comprises following composition by mass percentage:
Polyamines: 4%～22%, alkali: 10%～25%, chloroparaffin: 2%～10%, CS
2: 8%～35%, alcohol: 0～5%.
Described heavy metal ion complexing agent preferably comprises following composition by mass percentage:
Polyamines: 10%, alkali: 20%, chloroparaffin: 5%, CS
2: 25%, alcohol: 2%.
Described polyamines is at least a in quadrol, diethylenetriamine, triethylene tetramine or the tetraethylene pentamine;
Preferably, described polyamines be quadrol with diethylenetriamine, triethylene tetramine or tetraethylene pentamine in a kind of mixture that obtains that mixes;
Preferred, described polyamines is a kind of by mass ratio 1 in quadrol and diethylenetriamine, triethylene tetramine or the tetraethylene pentamine: the mixture that (10～20) proportioning obtains;
Preferred, described polyamines is the mixture of quadrol and tetraethylene pentamine;
Described alkali is at least a in sodium hydroxide or the potassium hydroxide;
Described chloroparaffin is at least a in ethylene dichloride, propylene dichloride or the epoxy chloropropane;
Described alcohol is at least a in methyl alcohol or the ethanol;
Preferably, described chloroparaffin is epoxy chloropropane;
Preferably, described alkali is sodium hydroxide;
Preferably, described alcohol is ethanol.
The preparation method of described heavy metal ion complexing agent comprises the steps:
(1) alkali of getting mass percent 10%～25% is dissolved in and makes alkali lye in the deionized water, and gained alkali lye is divided into A alkali lye and B alkali lye two portions;
(2) get A alkali lye in reaction vessel, in 20～35 ℃ of stirrings, then add the polyamines of mass percent 4%～22% and the chloroparaffin of mass percent 2%～10% successively; After chloroparaffin adds, be warming up to 50～90 ℃, reaction 2～4h is cooled to 20～35 ℃ subsequently, obtains mixed solution;
(3) after B alkali lye being joined in the described mixed solution of step (2), add the CS of mass percent 8%～35%
2With the alcohol of mass percent 0～5%, stirring reaction 2～12h obtains product liquid, the complexing of metal ion agent of attaching most importance to.
Wherein,
The volume of the A alkali lye described in the step (1) is 0～2/3 of described alkali lye cumulative volume amount; The remainder of described alkali lye is B alkali lye;
The rotating speed of the stirring described in the step (2) is 500～1500 rev/mins;
The interpolation speed of the chloroparaffin described in the step (2) is 2%～5% of per minute interpolation chloroparaffin total mass;
CS described in the step (3)
2Can be dissolved in described alcohol earlier and be prepared as CS
2Add with 1mL/ minute speed behind the solution;
Stirring reaction described in the step (3) is preferably earlier with 500～1500 rev/mins stirring velocity stirring reaction 2h, is warmed up to 50～70 ℃ of reaction 1～2h subsequently, is down to 20～35 ℃ subsequently;
Product liquid described in the step (3) becomes solid product 40～60 ℃ of following vacuum-dryings.
The application of described heavy metal ion complexing agent in waste water heavy metal contamination control, according to characteristics such as the kind of handling heavy metal in the waste water, concentration, the heavy metal ion complexing agent that adds respective amount stirs precipitation and can remove heavy metal ion in the water.
The formulation of described heavy metal ion complexing agent is liquid form or solid crystallization way.
Inventive principle
The ultimate principle that heavy metal ion complexing agent of the present invention is removed heavy metal is: synthetic novel heavy metal ion complexing agent contain a large amount of dithiocarbamic acid root functional groups and a certain amount of-OH ,-NH
2Deng functional group, there is very strong adsorption in this class functional group to heavy metal cation, and in addition, the negative charge that self has also has adsorption to heavy metal cation.Sulphur atom electronegativity in the dithiocarbamic acid root functional group is little, radius is big and contain lone electron pair, volatile de-electronation and the generation negative electric field that easily polarizes, can catch positively charged ion and tend to into key according to ligand field theory dithiocarbamic acid root functional group, with the heavy metal ion M of divalence
2+(as Ni
2+Deng) formation plane square or positive tetrahedron configuration or octahedra configuration, because the sterie configuration that complexing agent is less with different metal ion formation tension force, so the dithiocar-bamate complex compound of complexing agent and metal ion reaction generation has advantages of higher stability and is easy to precipitation.Simultaneously, the heavy metal ion enveloping agent solution is basic solution, and the existence of a large amount of hydroxide ions can generate precipitation of hydroxide with the heavy metal cation reaction, removes with the coprecipitation of dithiocar-bamate flco subsequently.In addition, also contain a certain amount of S in the heavy metal ion enveloping agent solution
2-, can generate sulfide precipitation with the heavy metal cation reaction, heavy metal ion is also had certain removal effect.
Wherein, the concrete principal reaction equation of above-mentioned heavy metal ion complexing agent removal heavy metal is:
Oxyhydroxide and sulfide to the removal reaction equation of heavy metal are in the heavy metal ion complexing agent:
M
2++2OH
-→M(OH)
2↓
M
2++S
2-→MS↓。
The present invention compared with prior art has following advantage and beneficial effect:
1) raw material sources are extensive, and are cheap, and preparation technology, transportation, storage and use are simple, and production cost is low;
2) heavy metal ion complexing agent provided by the invention all has good effect of removing, clearance 〉=99% to common heavy metal ion (Hg, Cd, Pb, Ni etc.); And its to the suspended substance in the waste water (suspended solids, SS), colloid thing and colourity etc. also have certain removal effect, produced simultaneously throw out is stable, secondary pollution is little; To use pH value to waste water to require wide for this heavy metal ion complexing agent in addition, and wastewater pH 〉=3 can reach higher removal effect.
3) heavy metal ion complexing agent provided by the invention can be widely used in the heavy metal containing wastewater treatment of industrial production generations such as China's chemical industry, non-ferrous metal selecting and purchasing and smelting, battery manufacturing, plating, printing and dyeing, pottery, plastics, need not increase new equipment and structures in the use, only utilize existing water conditioner preparation add-on system to get final product application implementation, use simply, applied range, adaptability are strong.
Embodiment
The present invention is further detailed explanation below in conjunction with specific embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: triethylene tetramine 100g accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the aforementioned alkali lye of getting cumulative volume 1/3 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g triethylene tetramine, slow Dropwise 5 0g epoxy chloropropane subsequently, the per minute rate of addition is 4% of total mass.After chloroparaffin adds, be warming up to 60 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 25 ℃ after reaction finishes.Add remaining 2/3 alkali lye, slowly drip 250g CS with 1mL/ minute speed subsequently
2Solution, reaction 6h gets orange heavy metal ion complexing agent 1000g.
Prepare the simulated wastewater 1L of different pH values, heavy metal Cd content is 50mg/L, and the pH value is respectively 1.5,3,5,7,9,10.Getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 2ml adds in the simulated wastewater of preparing, subsequently on six stirrers according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Cd concentration with ICP-MS and be respectively 10.77,6.53,0.81,0.15,0.04,0.006mg/L, clearance is respectively 78.5%, 87.94%, 98.38%, 99.7%, 99.92%, 99.99%, record reaction back pH value of solution value with pH meter simultaneously and be respectively 6.7,6.9,7.1,7.3,7.4,7.7.
Embodiment 2
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 40g accounts for 4% of total amount; Potassium hydroxide 100g accounts for 10% of total amount; Ethylene dichloride 20g accounts for 2% of total amount; CS
280g accounts for 8% of total amount; Methyl alcohol 20g accounts for 2% of total amount, and deionized water 740g accounts for 74% of total amount.
Earlier 100g potassium hydroxide is dissolved in the 740g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/4 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 20 ℃ water-bath, stirs, and mixing speed is 500 rev/mins.Slowly add the 40g quadrol simultaneously under stirring condition, slowly drip the ethylene dichloride of 20g subsequently, the per minute rate of addition is 2% of total amount, after chloroparaffin adds, be warming up to 50 ℃, reaction 4h, this moment, solution was creamy white thickly, was down to 20 ℃ after reaction finishes.Add remaining 3/4 alkali lye subsequently, slowly drip 80g CS with 1mL/ minute speed
2With the mixing solutions that 20g methyl alcohol forms, reaction 8h gets orange heavy metal ion complexing agent 1000g.
Get actual Production of Ceramics waste water 1L, pH value 5.6, ss suspended solid is 185mg/L, heavy metal Cd content is 50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 50ml deionized water, be mixed with the heavy metal ion enveloping agent solution, get above-mentioned heavy metal ion enveloping agent solution 2ml and add in the waste water, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settles afterwards to get supernatant liquor behind the 30min to record residue Cd concentration with ICP-MS be 0.5mg/L, and clearance is 99%, recording reaction back pH value of solution value with pH meter is 7.2, and ss suspended solid is 105mg/L.
Embodiment 3
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: diethylenetriamine 80g accounts for 8% of total amount; Sodium hydroxide 150g accounts for 15% of total amount; Propylene dichloride 40g accounts for 4% of total amount; CS
2100g accounts for 10% of total amount; Ethanol 50g accounts for 5% of total amount, and deionized water 560g accounts for 56% of total amount.Earlier 150g sodium hydroxide is dissolved in the 560g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 25 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Slowly add the 80g diethylenetriamine simultaneously under stirring condition, slowly drip the propylene dichloride of 40g subsequently, the per minute rate of addition is 3% of total amount, after chloroparaffin adds, be warming up to 60 ℃, reaction 4h, this moment, solution was creamy white thickly, was down to 25 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 10g CS with 1mL/ minute speed
2With the mixing solutions that 50g ethanol forms, reaction 6h gets orange heavy metal ion complexing agent 1000g.
Get actual Production of Ceramics waste water 1L, pH value 5.6, ss suspended solid is 185mg/L, heavy metal Ni content is 150mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 50ml deionized water, be mixed with the heavy metal ion enveloping agent solution, get above-mentioned heavy metal ion enveloping agent solution 3ml and add in the waste water, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settles afterwards to get supernatant liquor behind the 30min to record residue Ni concentration with ICP-MS be 0.8mg/L, and clearance is 99.5%, recording reaction back pH value of solution value with pH meter is 7.4, and ss suspended solid is 81.0mg/L.
Embodiment 4
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: triethylene tetramine 120g accounts for 12% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 60g accounts for 6% of total amount; CS
2150g accounts for 15% of total amount; Ethanol 50g accounts for 5% of total amount, and deionized water 420g accounts for 42% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 420g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 2/3 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 30 ℃ water-bath, stirs, and mixing speed is 1000 rev/mins.Slowly add the 120g triethylene tetramine simultaneously under stirring condition, slowly drip the epoxy chloropropane of 60g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 70 ℃, reaction 3.5h, this moment, solution was creamy white thickly, was down to 30 ℃ after reaction finishes.Add remaining 1/3 alkali lye subsequently, slowly drip 150g CS with 1mL/ minute speed
2With the mixing solutions that 50g ethanol forms, reaction 4h gets orange heavy metal ion complexing agent 1000g.
Get actual Production of Ceramics waste water 1L, pH value 5.6, ss suspended solid is 185mg/L, heavy metal Pb content is 50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, get above-mentioned heavy metal ion enveloping agent solution 1.5ml and add in the waste water, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settles afterwards to get supernatant liquor behind the 30min to record residue Pb concentration with ICP-MS be 0.003mg/L, and clearance is 99.99%, recording reaction back pH value of solution value with pH meter is 7.5, and ss suspended solid is 75.3mg/L.
Embodiment 5
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: triethylene tetramine 100g accounts for 10% of total amount; Sodium hydroxide 240g accounts for 24% of total amount; Epoxy chloropropane 60g accounts for 6% of total amount; CS
2200g accounts for 20% of total amount; Ethanol 0g accounts for 0% of total amount, and deionized water 400g accounts for 40% of total amount.
Earlier 240g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution.At first the 100g triethylene tetramine is placed the three-necked flask that has agitator and reflux exchanger, three-necked flask places 30 ℃ water-bath, stirs, and mixing speed is 1000 rev/mins.Slowly drip the epoxy chloropropane of 60g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, is warming up to 80 ℃, reaction 2h, and this moment, solution was creamy white thickly, was down to 30 ℃ after reaction finishes.Add sodium hydroxide solution, slowly drip 200g CS with 1mL/ minute speed subsequently
2Solution, first stirring reaction 2h is warming up to 60 ℃ of reaction 2h subsequently, gets sorrel heavy metal ion complexing agent 1000g.
Get actual Production of Ceramics waste water 1L, pH value 5.6, ss suspended solid is 185mg/L, heavy metal Cd content is 50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, get above-mentioned heavy metal ion enveloping agent solution 2.5ml and add in the waste water, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settles afterwards to get supernatant liquor behind the 30min to record residue Cd concentration with ICP-MS be 0.001mg/L, and clearance is 99.99%, recording reaction back pH value of solution value with pH meter is 7.5, and ss suspended solid is 84.6mg/L.
Embodiment 6
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: tetraethylene pentamine 150g accounts for 15% of total amount; Sodium hydroxide 250g accounts for 25% of total amount; Epoxy chloropropane 80g accounts for 8% of total amount; CS
2200g accounts for 20% of total amount; Deionized water 320g accounts for 32% of total amount.
Earlier 250g sodium hydroxide is dissolved in the 320g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 35 ℃ water-bath, stirs, and mixing speed is 1500 rev/mins.Slowly add the 150g tetraethylene pentamine simultaneously under stirring condition, slowly drip the epoxy chloropropane of 80g subsequently, the per minute rate of addition is 5% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 3h, this moment, solution was creamy white thickly, was down to 35 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 200g CS with 1mL/ minute speed
2Solution, reaction 12h gets orange heavy metal ion complexing agent 1000g.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Hg content is 50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 1.5ml adds in the simulated wastewater of preparing, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settles afterwards to get supernatant liquor behind the 30min to record residue Hg concentration with ICP-MS be 0.01mg/L, clearance is 99.98%, and recording reaction back pH value of solution value with pH meter is 7.3.
Embodiment 7
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 10g+ triethylene tetramine 200g (quadrol and triethylene tetramine mass ratio are 1: 20) accounts for 21% of total amount; Sodium hydroxide 120g accounts for 12% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2300g accounts for 30% of total amount; Deionized water 320g accounts for 32% of total amount.
Earlier 120g sodium hydroxide is dissolved in the 320g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 30 ℃ water-bath, stirs, and mixing speed is 1500 rev/mins.Under stirring condition, slowly add simultaneously the 210g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 90 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 30 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 300g CS with 1mL/ minute speed
2Solution, first stirring reaction 2h is warming up to 50 ℃ of reaction 2h subsequently, gets sorrel heavy metal ion complexing agent 1000g.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 50ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 4ml adds in the simulated wastewater of preparing, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.02,0.05,0.3,0.08mg/L, clearance is respectively 99.96%, 99.9%, 99.8%, 99.8%, recording reaction back pH value of solution value with pH meter is 7.1.
Embodiment 8
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 20g+ tetraethylene pentamine 200g (mass ratio of quadrol and tetraethylene pentamine is 1: 10) accounts for 22% of total amount; Sodium hydroxide 150g accounts for 15% of total amount; Epoxy chloropropane 80g accounts for 8% of total amount; CS
2350g accounts for 35% of total amount; Deionized water 200g accounts for 20% of total amount.
Earlier 150g sodium hydroxide is dissolved in the 200g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 1000 rev/mins.Slowly add the 220g polyamine mixture simultaneously under stirring condition, slowly drip the epoxy chloropropane of 80g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 28 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, with the slow Dropwise 35 0g of 1mL/ minute speed CS
2Solution, reaction 12h gets orange heavy metal ion complexing agent 1000g.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 4ml adds in the simulated wastewater of preparing, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.007,0.005,0.08,0.02mg/L, clearance is respectively 99.98%, 99.99%, 99.99%, 99.96%, recording reaction back pH value of solution value with pH meter is 7.1.
Embodiment 9
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 9.1g+ tetraethylene pentamine 90.9g (mass ratio of quadrol and tetraethylene pentamine is 1: 10) accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 28 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 250g CS with 1mL/ minute speed
2Solution, first stirring reaction 2h is warming up to 70 ℃ of reaction 1h subsequently, gets sorrel heavy metal ion complexing agent 1000g.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 4ml adds in the simulated wastewater of preparing, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.02,0.01,0.15,0.09mg/L, clearance is respectively 99.96%, 99.98%, 99.9%, 99.8%, recording reaction back pH value of solution value with pH meter is 7.3.
Embodiment 10
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 6.3g+ diethylenetriamine 93.7g (mass ratio of quadrol and diethylenetriamine is 1: 15) accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 28 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 250g CS with 1mL/ minute speed
2Solution, reaction 6h gets orange heavy metal ion complexing agent 1000g.
Power taking waste electroplating 1L, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 3ml adds in the waste water, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.05,0.03,0.3,0.15mg/L, clearance is respectively 99.9%, 99.94%, 99.8%, 99.7%, recording reaction back pH value of solution value with pH meter is 7.3.
Embodiment 11
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 6.3g+ tetraethylene pentamine 93.7g (mass ratio of quadrol and tetraethylene pentamine is 1: 15) accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 28 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 250g CS with 1mL/ minute speed
2Solution, reaction 6h gets orange heavy metal ion complexing agent 1000g.Subsequently the heavy metal ion complexing agent is placed the vacuum forced air drying mutually, freeze-day with constant temperature 12h under 40 ℃ condition gets the orange xln.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, taking by weighing heavy metal ion complexing agent 50mg drops in the electroplating wastewater, according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.05,0.03,0.30,0.13mg/L, clearance is respectively 99.9%, 99.94%, 99.8%, 99.7%, recording reaction back pH value of solution value with pH meter is 7.2.
Embodiment 12
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 9.1g+ triethylene tetramine 90.9g (mass ratio of quadrol and triethylene tetramine is 1: 10) accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 28 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 250g CS with 1mL/ minute speed
2Solution, reaction 6h gets orange heavy metal ion complexing agent 1000g.Subsequently the heavy metal ion complexing agent is placed the vacuum forced air drying mutually, freeze-day with constant temperature 10h under 60 ℃ condition gets the orange xln.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, taking by weighing heavy metal ion complexing agent 60mg drops in the electroplating wastewater, according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.10,0.08,0.50,0.30mg/L, clearance is respectively 99.8%, 99.84%, 99.7%, 99.4%, recording reaction back pH value of solution value with pH meter is 7.4.
Embodiment 13
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 6.3g+ triethylene tetramine 93.7g (mass ratio of quadrol and triethylene tetramine is 1: 15) accounts for 10% of total amount; Sodium hydroxide 240g accounts for 24% of total amount; Epoxy chloropropane 60g accounts for 6% of total amount; CS
2200g accounts for 20% of total amount; Deionized water 400g accounts for 40% of total amount.
Earlier 240g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution.At first the 100g polyamine mixture is placed the three-necked flask that has agitator and reflux exchanger, three-necked flask places 30 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.The slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, is warming up to 80 ℃, reaction 2h, this moment, solution was creamy white thickly, and reaction is down to 28 ℃ after finishing.Add whole sodium hydroxide solutions subsequently, slowly drip 200g CS with 1mL/ minute speed
2Solution, reaction 6h gets orange heavy metal ion complexing agent 1000g.Subsequently the heavy metal ion complexing agent is placed the vacuum forced air drying mutually, freeze-day with constant temperature 10h under 50 ℃ condition gets the orange xln.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, taking by weighing heavy metal ion complexing agent 60mg drops in the electroplating wastewater, according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0.12,0.09,0.50,0.33mg/L, clearance is respectively 99.8%, 99.82%, 99.7%, 99.3%, recording reaction back pH value of solution value with pH meter is 7.4.
Embodiment 14
The required raw materials for production of heavy metal ion complexing agent of preparation 1Kg: quadrol 6.3g+ triethylene tetramine 93.7g (mass ratio of quadrol and tetraethylene pentamine is 1: 15) accounts for 10% of total amount; Sodium hydroxide 200g accounts for 20% of total amount; Epoxy chloropropane 50g accounts for 5% of total amount; CS
2250g accounts for 25% of total amount; Ethanol 20g accounts for 2% of total amount; Deionized water 380g accounts for 38% of total amount.
Earlier 200g sodium hydroxide is dissolved in the 400g deionized water in the preparation process and makes sodium hydroxide solution, the alkali lye of getting cumulative volume 1/2 places the three-necked flask of belt stirrer and reflux exchanger, three-necked flask places 28 ℃ water-bath, stirs, and mixing speed is 800 rev/mins.Under stirring condition, slowly add simultaneously the 100g polyamine mixture, the slow epoxy chloropropane of Dropwise 5 0g subsequently, the per minute rate of addition is 4% of total amount, after chloroparaffin adds, be warming up to 60 ℃, reaction 2h, this moment, solution was creamy white thickly, was down to 25 ℃ after reaction finishes.Add remaining 1/2 alkali lye subsequently, slowly drip 270g CS with 1mL/ minute speed
2With the mixing solutions of ethanol, reaction 6h gets orange heavy metal ion complexing agent 1000g.
Preparation analog electrical waste electroplating 1L, the pH value is 7.0, heavy metal Pb, Cd, Ni, Hg content is respectively 50,50,150,50mg/L, getting 10g heavy metal ion complexing agent is dissolved in the 100ml deionized water, be mixed with the heavy metal ion enveloping agent solution, getting above-mentioned heavy metal ion enveloping agent solution 3ml adds in the simulated wastewater of preparing, subsequently according to 300rpm * 1min, slow-speed 60rpm * 5min, 45rpm * 5min, the program of 25rpm * 5min is carried out stirring reaction, staticly settle afterwards and get supernatant liquor behind the 30min and record residue Pb with ICP-MS, Cd, Ni, Hg content is respectively 0,0.003,0.13,0.08mg/L, clearance is respectively 100%, 99.99%, 99.91%, 99.84%, recording reaction back pH value of solution value with pH meter is 7.3.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. heavy metal ion complexing agent is characterized in that comprising following composition by mass percentage:
Polyamines: 4%～22%, alkali: 10%～25%, chloroparaffin: 2%～10%, CS
2: 8%～35%, alcohol: 0～5%;
Described polyamines is at least a in quadrol, diethylenetriamine, triethylene tetramine or the tetraethylene pentamine;
Described alkali is at least a in sodium hydroxide or the potassium hydroxide;
Described chloroparaffin is at least a in ethylene dichloride, propylene dichloride or the epoxy chloropropane;
Described alcohol is at least a in methyl alcohol or the ethanol;
The preparation method of described heavy metal ion complexing agent comprises the steps:
(1) alkali of getting mass percent 10%～25% is dissolved in the deionized water, obtains alkali lye, and gained alkali lye is divided into A alkali lye and B alkali lye two portions;
(2) get A alkali lye in reaction vessel, in 20～35 ℃ of stirrings, then add the polyamines of mass percent 4%～22% and the chloroparaffin of mass percent 2%～10% successively; After chloroparaffin adds, be warming up to 50～90 ℃, reaction 2～4h is cooled to 20～35 ℃ subsequently, obtains mixed solution;
(3) after B alkali lye being joined in the described mixed solution of step (2), add the CS of mass percent 8%～35%
2With the alcohol of mass percent 0～5%, stirring reaction 2～12h obtains product liquid, the complexing of metal ion agent of attaching most importance to.
2. heavy metal ion complexing agent according to claim 1 is characterized in that comprising following composition by mass percentage:
Polyamines: 10%, alkali: 20%, chloroparaffin: 5%, CS
2: 25%, alcohol: 2%.
3. heavy metal ion complexing agent according to claim 1 is characterized in that: described polyamines be quadrol with diethylenetriamine, triethylene tetramine or tetraethylene pentamine in a kind of mixture that obtains that mixes;
Described chloroparaffin is epoxy chloropropane;
Described alkali is sodium hydroxide;
Described alcohol is ethanol.
4. heavy metal ion complexing agent according to claim 3 is characterized in that: polyamines is a kind of by mass ratio 1 in quadrol and diethylenetriamine, triethylene tetramine or the tetraethylene pentamine: the mixture that (10～20) proportioning obtains.
5. heavy metal ion complexing agent according to claim 3, it is characterized in that: described polyamines is the mixture of quadrol and tetraethylene pentamine.
6. heavy metal ion complexing agent according to claim 1 is characterized in that:
The volumetric usage of the A alkali lye described in the step (1) be described alkali lye cumulative volume 0～2/3;
The rotating speed of the stirring described in the step (2) is 500～1500 rev/mins;
The interpolation speed of the chloroparaffin described in the step (2) is 2%～5% of chloroparaffin total mass for the per minute addition;
CS described in the step (3)
2Be dissolved in described alcohol earlier and prepare CS
2Add with 1mL/ minute speed behind the solution;
Stirring reaction described in the step (3) is earlier with 500～1500 rev/mins stirring velocity stirring reaction 2h, is warmed up to 50～70 ℃ of reaction 1～2h subsequently, is down to 20～35 ℃ subsequently;
Product liquid described in the step (3) becomes solid product 40～60 ℃ of following vacuum-dryings.
7. the application of each described heavy metal ion complexing agent of claim 1～6 in waste water heavy metal contamination control, it is characterized in that: according to the kind of handling heavy metal in the waste water, the characteristics of concentration, stir behind the heavy metal ion complexing agent of adding respective amount to remove and precipitate the heavy metal ion that to remove in the water; The formulation of described heavy metal ion complexing agent is liquid form or solid crystallization way.
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| CN102921278B (en) * | 2012-10-24 | 2015-04-29 | 环境保护部华南环境科学研究所 | Method for collaboratively controlling multi-pollutants produced from waste incineration smokes |
| CN103030205B (en) * | 2012-12-12 | 2014-02-19 | 刘进龙 | Method for preparing dangerous heavy metal removing agent in electroplating wastewater and application thereof |
| CN103011370B (en) * | 2012-12-24 | 2014-05-07 | 广西博世科环保科技股份有限公司 | Preparation method for polyamine heavy metal ion chelating agent |
| CN103143328B (en) * | 2013-03-07 | 2015-12-02 | 西安科技大学 | A kind of preparation method of heavy metal chelating adsorbent |
| CN103663659A (en) * | 2013-12-26 | 2014-03-26 | 山东华升化工科技有限公司 | Composite flocculant and preparation method thereof |
| CN104147907B (en) * | 2014-08-26 | 2016-05-25 | 深圳市百欧森环保科技开发有限公司 | A kind of mercury agent for capturing and its preparation method and application |
| CN104528910A (en) * | 2014-12-18 | 2015-04-22 | 淄博金鼎光电科技有限公司 | Synthetic process of heavy metal chelating agent |
| RU2590537C1 (en) * | 2015-02-05 | 2016-07-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Иркутский государственный университет путей сообщения" (ФГБОУ ВО ИрГУПС) | Use of poly(3-oxapentylenedisulphide) for extraction of heavy metals from aqueous solutions |
| CN105021558B (en) * | 2015-08-07 | 2017-07-14 | 齐鲁工业大学 | A kind of fig fruit lead cadmium assay method |
| CN105777598A (en) * | 2016-03-18 | 2016-07-20 | 常州大学 | Method for synthesizing organic precipitants (AHD) capable of removing silver ions in industrial wastewater |
| CN106807029A (en) * | 2016-12-30 | 2017-06-09 | 上海丰信环保科技有限公司 | A kind of component chelating agent of high-efficiency refuse incinerating flyash, heavy metal three |
| CN110451622B (en) * | 2019-08-12 | 2021-01-26 | 北京师范大学 | Heavy metal removal preparation and synthesis method and application thereof |
| CN109721127A (en) * | 2019-01-31 | 2019-05-07 | 环境保护部华南环境科学研究所 | Heavy metal containing wastewater treatment agent |
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