CN109704974B - Heavy metal chelating agent and preparation method and application thereof - Google Patents
Heavy metal chelating agent and preparation method and application thereof Download PDFInfo
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- CN109704974B CN109704974B CN201811614682.XA CN201811614682A CN109704974B CN 109704974 B CN109704974 B CN 109704974B CN 201811614682 A CN201811614682 A CN 201811614682A CN 109704974 B CN109704974 B CN 109704974B
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Abstract
The invention relates to a heavy metal chelating agent and a preparation method and application thereof. The preparation method of the heavy metal chelating agent has strong operability and simple process, and the prepared chelating agent contains more chelating sites, has high reaction activity and high chelating performance, and can efficiently precipitate heavy metals.
Description
Technical Field
The invention relates to the technical field of metal chelating agents, in particular to a heavy metal chelating agent, a preparation method and application thereof, and particularly relates to a heavy metal chelating agent with high reactivity and high chelating performance, and a preparation method and application thereof.
Background
The waste incineration fly ash is dark gray or grey-white fine powder, the particle size of 90% of fly ash particles is less than 300 μm, the fly ash is often rich in heavy metals such as copper, chromium, lead, zinc, cadmium, nickel, tin, manganese, mercury, arsenic and the like and corresponding oxides thereof, and how to effectively treat the heavy metals in the waste incineration fly ash is the concern of people. The chemical chelation method is a heavy metal fly ash treatment method with better effect and lower cost, and can be suitable for the treatment of large-scale fly ash. Based on this, the prior art discloses a number of synthetic polymeric chelants for fly ash treatment, such as dithiocarbamate chelants, ethylenediaminetetraacetic acid (EDTA) chelants, and the like; in addition, some natural chelating agents such as citric acid, tartaric acid, oxalic acid and the like are used in the traditional treatment method, but a series of problems such as difficult heavy metal recovery, incomplete chelation, unsatisfactory settling effect and the like are exposed. The main reason is that the chelating agent has single chelating function and few chelating points, so the formed chelating agent has small volume, small chelating area and poor sedimentation performance, and can achieve better effect only by maintaining large excessive concentration.
CN103172159A discloses a preparation method of a compound heavy metal chelating agent, which comprises the following steps: 1) adding water and polyamine compound into a reaction kettle and uniformly stirring; 2) slowly dripping halogenated alkylene oxide into a reaction kettle and keeping the temperature not to exceed 50 ℃; 3) heating the reaction kettle to 50-90 ℃, and continuously stirring and reacting for 2-6 hours at the temperature; 4) cooling water is introduced into the reaction kettle to reduce the temperature to 25-35 ℃, and then 1.3.5-triazine-2.4.6-trithiol trisodium salt is added and stirred for 0.5-1 hour to obtain the compound heavy metal chelating agent. The heavy metal chelating agent prepared by the invention reserves the environment-friendly advantage of TMT-15, overcomes the defects of small floc and difficult precipitation and filtration, and can ensure that the content of heavy metal in effluent is lower than the national standard under the condition of not additionally adding a polyacrylamide flocculant in the follow-up process. However, the chelating agent has the disadvantage of fewer chelating points, and the sedimentation performance of the chelating agent is limited.
CN108379765A discloses a heavy metal chelating agent and a preparation method thereof, wherein the heavy metal chelating agent is composed of 10-25 parts by weight of sodium ferulate, 5-15 parts by weight of sodium phosphate, 5-20 parts by weight of EDTA, 0.5-1 part by weight of polycarboxylic acid and 5-10 parts by weight of glucose. Adding the raw materials into softened water, uniformly stirring, standing for 20 hours, and then carrying out solid-liquid separation to obtain separated liquid, namely the heavy metal chelating agent. The heavy metal chelating agent can be used at different temperatures, has a good chelating effect on fly ash with the pH range of 3-11, is environment-friendly, safe and nontoxic, has stable properties of chelated products, and can not release heavy metals again under the acidity and time specified by relevant standards. However, the method still has the defects of few chelating points, small formed chelating volume, small chelating area, poor settling property and the like.
CN106955451A discloses a waste incineration fly ash heavy metal chelating agent, which comprises a compound chelating agent and a sodium hydroxide solution mixed according to the weight ratio of 1 (2-3), wherein the compound chelating agent comprises the following components in percentage by weight: organic chelating agent: 60 to 90 percent; inorganic chelating agent: 10 to 40 percent; the organic chelating agent is dithio-carbamate, and is selected from one or more of zinc diethyl dithiocarbamate, zinc dimethyl dithiocarbamate, sodium dibutyl dithiocarbamate or sodium dibenzyl dithiocarbamate; the inorganic chelating agent is selected from one or two of sodium sulfide and sodium phosphate. The heavy metal chelating agent can reduce the leaching concentration of heavy metals, ensures that a fly ash solidified sample block meets the limit value of the leaching concentration, but has few chelating points, small formed chelating volume and small chelating area, and can not effectively settle the heavy metals in the garbage fly ash.
Therefore, it is significant to develop a heavy metal chelating agent which contains multiple chelating sites, has high reactivity and high chelating performance and can effectively precipitate the heavy metals in the garbage fly ash.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heavy metal chelating agent, a preparation method and application thereof, and particularly provides a heavy metal chelating agent with high reactivity and high chelating performance, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of a heavy metal chelating agent, which comprises the following steps:
(1) using polyene polyamine molecules as raw materials, and carrying out unilateral protection on terminal primary amine of the polyene polyamine molecules by using di-tert-butyl dicarbonate to obtain unilateral-protected polyene polyamine;
(2) carrying out chain extension crosslinking reaction on the unilateral protected polyene polyamine obtained in the step (1) and a chain extender to obtain crosslinked polyene polyamine;
(3) removing the unilateral protection of the crosslinked polyene polyamine in the step (2) to obtain deprotected crosslinked polyene polyamine;
(4) and (4) carrying out xanthation acylation reaction on the deprotected crosslinked polyene polyamine obtained in the step (3) and carbon disulfide to obtain the heavy metal chelating agent.
The preparation method of the heavy metal chelating agent comprises the steps of firstly protecting a part of amino groups on a polyene polyamine molecular chain by using di-tert-butyl dicarbonate so as not to participate in subsequent crosslinking reaction, and after the crosslinking reaction is finished, removing the protection of the amino groups so that the final crosslinked polyene polyamine has more reaction sites with carbon disulfide and also has more heavy metal chelating sites, thereby greatly improving the chelating performance.
In the present invention, the polyene polyamine molecule in step (1) includes any one or a combination of at least two of ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, and the combination of the two includes ethylenediamine and diethylenetriamine, diethylenetriamine and triethylenetetramine, triethylenetetramine and tetraethylenepentamine, and the like.
Preferably, the specific method for unilateral protection of terminal primary amine of the polyene polyamine molecule by using di-tert-butyl dicarbonate in the step (1) is as follows:
dissolving polyene polyamine molecule in alkali solution, and adding di-tert-butyl dicarbonate to make reaction.
Preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the molar ratio of the base to the polyene polyamine molecule is 2 (0.8-15), such as 2:0.8, 2:1, 2:3, 2:5, 2:8, 2:10, 2:12, 2:15, and the like.
Preferably, the solvent of the alkali solution is deionized water.
Preferably, the concentration of the alkali solution is 45% to 90% by mass, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% by mass.
Preferably, the molar ratio of di-tert-butyl dicarbonate to polyene polyamine molecule is (0.9-1.3):1, such as 0.9:1, 1.0:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1 or 1.3: 1.
Preferably, the manner of adding the di-tert-butyl dicarbonate is dropwise.
Preferably, the di-tert-butyl dicarbonate is added while stirring.
Preferably, the temperature at which di-tert-butyl dicarbonate is added is 0 ℃.
Preferably, the reaction temperature is 20-30 ℃, such as 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.
Preferably, the reaction time is 2-3h, such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 3h, etc.
In the present invention, the chain extender of step (2) includes a dihaloalkane and/or a haloalkylene oxide.
Preferably, the dihaloalkane comprises any one of 1, 2-dichloroethane, 1, 3-dichloropropane, 1, 4-dichlorobutane or 1, 2-dibromoethane or a combination of at least two of the two, such as 1, 2-dichloroethane and 1, 3-dichloropropane, 1, 3-dichloropropane and 1, 4-dichlorobutane, 1, 4-dichlorobutane and 1, 2-dibromoethane, and the like.
Preferably, the haloalkylene oxide comprises a chloroalkylene oxide and/or a bromoalkylene oxide.
Preferably, the molar ratio of the chain extender to the one-side protected polyene polyamine molecule in step (2) is 1 (0.1-3), such as 1:0.1, 1:0.2, 1:0.4, 1:0.6, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5 or 1:3, etc.
The molar ratio of the chain extender and the single-side protected polyene polyamine molecule is selected from the range of 1 (0.1-3) specifically, because the precipitation can be generated when the molar ratio exceeds the range, and meanwhile, the branched chain products are increased, so that the steric hindrance is increased when heavy metal is chelated, and the chelating performance is poor; if the content is less than the range, the reaction is incomplete, the crosslinking is incomplete, the molecular weight of the formed chelating agent is smaller, and the performance of heavy metal precipitation is poorer.
Preferably, the specific method for chain-extension crosslinking reaction of the unilateral protected polyene polyamine and the chain extender in the step (2) is as follows:
adding a chain extender into an alkaline solution dissolved with unilateral protection polyene polyamine to carry out chain extension crosslinking reaction.
Preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the solvent of the alkali solution is deionized water.
Preferably, the concentration of the alkali solution is 45% to 90% by mass, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% by mass.
Preferably, the manner of adding the chain extender is dropwise.
Preferably, the chain extender is added while stirring.
Preferably, the temperature at which the chain extender is added is 0 ℃.
Preferably, the reaction temperature is 20-30 ℃, such as 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃.
Preferably, the reaction time is 1-3h, such as 1h, 1.2h, 1.5h, 1.7h, 2h, 2.2h, 2.5h, 2.6h, 2.8h, 3h, or the like.
In the present invention, the unilateral protection removal of the crosslinked polyene polyamine described in the step (3) is performed in an acidic environment.
Preferably, the acidic environment has a pH of 3-4, such as 3, 3.2, 3.4, 3.6, 3.8, or 4, and the like.
Preferably, the acidic environment is obtained by adding an acid solution to the reaction system.
Preferably, the acid comprises any one of sulfuric acid, hydrochloric acid, acetic acid, trifluoroacetic acid or benzenesulfonic acid or a combination of at least two of the two, such as sulfuric acid and hydrochloric acid, hydrochloric acid and acetic acid, trifluoroacetic acid and benzenesulfonic acid, and the like.
Preferably, the solvent of the acid solution is deionized water.
Preferably, the acid solution has a concentration of 1% to 60%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, or 60%, etc.
Preferably, the mass ratio of the added amount of the acid solution to the crosslinked polyene polyamine is 1 (6-20), such as 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:17, 1:18, 1:19, 1:20, and the like.
Preferably, the deprotection temperature in step (3) is 20-30 deg.C, such as 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C or 30 deg.C etc.
Preferably, the deprotection time in step (3) is 4-6h, such as 4h, 4.2h, 4.5h, 4.7h, 5h, 5.2h, 5.5h, 5.6h, 5.8h or 6h, etc.
In the invention, the specific method for carrying out xanthation acylation reaction on the deprotected crosslinked polyene polyamine and carbon disulfide in the step (4) comprises the following steps:
and (4) adding an alkali solution into the reaction system obtained in the step (3), and then adding carbon disulfide for reaction.
Preferably, the molar ratio of the carbon disulfide to the deprotected crosslinked polyenepolyamine molecule is (0.5-6: 1), such as 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, or 6:1, and the like.
The molar ratio of the carbon disulfide and the deprotection crosslinking polyene polyamine is specially selected to be in the range of (0.5-6):1, because the carbon disulfide which does not participate in the reaction is deposited at the bottom of the solution and gradually volatilized in the subsequent use process, so that the atmospheric pollution is caused, and the adverse effect is caused to the health of operators and the environment; less than this range results in a less water soluble or even completely insoluble synthesized product, which results in the deactivation of the chelated heavy metals.
Preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the solvent of the alkali solution is deionized water.
Preferably, the concentration of the alkali solution is 45% to 90% by mass, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90% by mass.
Preferably, the manner of adding the carbon disulfide is dropwise.
Preferably, the carbon disulphide is added while stirring.
Preferably, the reaction is carried out in two steps: first reacting at 20-30 deg.C (such as 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C or 30 deg.C) for 1-3h (such as 1h, 1.2h, 1.5h, 1.7h, 2h, 2.2h, 2.5h, 2.6h, 2.8h or 3 h); and reacting at 60-65 deg.C (60 deg.C, 61 deg.C, 62 deg.C, 63 deg.C, 64 deg.C or 65 deg.C) for 2-3h (such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 3 h).
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) using polyene polyamine molecules as raw materials, using di-tert-butyl dicarbonate to carry out unilateral protection on terminal primary amine of the polyene polyamine molecules, wherein the molar ratio of the di-tert-butyl dicarbonate to the polyene polyamine molecules is (0.9-1.3):1, and carrying out reaction for 2-3h at 20-30 ℃ to obtain the unilateral protected polyene polyamine;
(2) under alkaline conditions, carrying out chain extension crosslinking reaction on the unilateral protected polyene polyamine obtained in the step (1) and a chain extender, wherein the molar ratio of the chain extender to the unilateral protected polyene polyamine molecule is 1 (0.1-3), and carrying out the reaction at 20-30 ℃ for 1-3h to obtain crosslinked polyene polyamine;
(3) under the acidic condition, removing the unilateral protection of the crosslinked polyene polyamine in the step (2), and reacting at 20-30 ℃ for 4-6h to obtain the deprotected crosslinked polyene polyamine;
(4) and (2) carrying out xanthation acylation reaction on the deprotected crosslinked polyene polyamine obtained in the step (3) and carbon disulfide under an alkaline condition, wherein the molar ratio of the carbon disulfide to the deprotected crosslinked polyene polyamine is (0.5-6):1, reacting for 1-3h at 20-30 ℃, and then reacting for 2-3h at 60-65 ℃ to obtain the heavy metal chelating agent.
In a second aspect, the present invention provides a heavy metal chelating agent prepared by the preparation method as described above.
In a third aspect, the present invention provides the use of a heavy metal chelating agent as described above for precipitating heavy metals.
Preferably, the heavy metal is the heavy metal in the waste incineration fly ash.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the heavy metal chelating agent has strong operability and simple process, and the prepared chelating agent contains more chelating sites, has high reaction activity and high chelating performance, can efficiently precipitate heavy metal, and has a heavy metal removal rate of 82.8-99.3%.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
Example 1
The embodiment provides a heavy metal chelating agent, and the preparation method comprises the following steps:
(1) dissolving diethylenetriamine and solid sodium hydroxide in deionized water at 0 ℃, slowly dripping di-tert-butyl dicarbonate into the deionized water through a dripping funnel under the condition of vigorous stirring, and recovering to 25 ℃ after dripping to react for 3 hours to obtain unilateral protected diethylenetriamine;
(2) cooling the reaction system to 0 ℃ by using an ice water bath again, then slowly dripping 1, 2-dichloroethane into the reaction system through a dripping funnel under the condition of vigorous stirring, controlling the dripping speed to be about 6s one drop, and recovering to 25 ℃ after finishing dripping to react for 2 hours to obtain crosslinked diethylenetriamine; the molar ratio of the 1, 2-dichloroethane to the unilaterally protected diethylenetriamine is 1: 2;
(3) slowly dripping 6N HCl solution into the reaction system until the pH value of the system reaches 4, and reacting for 5 hours at 25 ℃ after finishing dripping to obtain deprotected crosslinked diethylenetriamine;
(4) dropwise adding a saturated NaOH aqueous solution into the reaction system, then slowly dropwise adding carbon disulfide into the reaction system through a dropwise adding funnel under the condition of vigorous stirring, controlling the dropwise adding speed to be 4s and one drop, reacting for 2h at 25 ℃ after dropwise adding, then installing a reflux condenser tube, carrying out oil bath, heating and reacting for 2h at 65 ℃ to obtain the heavy metal chelating agent, and measuring the molecular weight range of the heavy metal chelating agent to be 20000-50000 daltons by using gel chromatography (GPC); the molar ratio of the carbon disulfide to the deprotection crosslinking diethylenetriamine molecule is 3: 1.
Example 2
The embodiment provides a heavy metal chelating agent, and a preparation method thereof comprises the following steps:
(1) dissolving triethylene tetramine and solid potassium hydroxide in deionized water at 0 ℃, slowly dripping di-tert-butyl dicarbonate into the deionized water through a dripping funnel under the condition of vigorous stirring, and recovering to 20 ℃ after dripping is finished to react for 3 hours to obtain unilaterally protected triethylene tetramine;
(2) cooling the reaction system to 0 ℃ by using an ice water bath again, then slowly dripping 1, 3-dichloropropane into the reaction system through a dripping funnel under the condition of vigorous stirring, controlling the dripping speed to be about 5s one drop, and recovering to 30 ℃ after dripping is finished to react for 1h to obtain crosslinked triethylene tetramine; the molar ratio of the 1, 3-dichloropropane to the unilateral protected triethylene tetramine is 1: 2;
(3) slowly dripping 6N acetic acid solution into the reaction system until the pH value of the system reaches 3, and reacting for 4 hours at 30 ℃ after finishing dripping to obtain deprotected crosslinked triethylene tetramine;
(4) dropwise adding a saturated KOH aqueous solution into the reaction system, then slowly dropwise adding carbon disulfide into the reaction system through a dropping funnel under vigorous stirring, controlling the dropping speed to be 4s and one drop, reacting for 1h at 30 ℃ after dropwise adding, then installing a reflux condenser tube, carrying out oil bath, heating and reacting for 3h at 60 ℃ to obtain the heavy metal chelating agent, and measuring the molecular weight range of the heavy metal chelating agent to be 40000 and 70000 daltons by using gel chromatography (GPC); the molar ratio of the carbon disulfide to the deprotected cross-linked triethylene tetramine molecule is 3: 1.
Example 3
The embodiment provides a heavy metal chelating agent, and the preparation method comprises the following steps:
(1) dissolving diethylenetriamine and solid sodium hydroxide in deionized water at 0 ℃, slowly dripping di-tert-butyl dicarbonate into the deionized water through a dripping funnel under the condition of vigorous stirring, and recovering to 30 ℃ after dripping to react for 2 hours to obtain unilateral protected diethylenetriamine;
(2) cooling the reaction system to 0 ℃ by using an ice water bath again, then slowly dripping 1, 4-dichlorobutane into the reaction system by using a dripping funnel under the condition of vigorous stirring, controlling the dripping speed to be about 5s one drop, and recovering to 20 ℃ after finishing dripping to react for 3 hours to obtain cross-linked diethylenetriamine; the molar ratio of the 1, 4-dichlorobutane to the unilateral protected diethylenetriamine is 1: 2;
(3) slowly dripping 6N HCl solution into the reaction system until the pH value of the system reaches 3.5, and reacting at 20 ℃ for 6h after finishing dripping to obtain deprotected crosslinked diethylenetriamine;
(4) dropwise adding a saturated NaOH aqueous solution into the reaction system, then slowly dropwise adding carbon disulfide into the reaction system through a dropwise adding funnel under the condition of vigorous stirring, controlling the dropwise adding speed to be 4s and one drop, reacting for 3h at 20 ℃ after dropwise adding, then installing a reflux condenser tube, carrying out oil bath, heating and reacting for 3h at 60 ℃ to obtain the heavy metal chelating agent, and measuring the molecular weight range of 20000-50000 dalton by using gel chromatography (GPC); the molar ratio of the carbon disulfide to the deprotection crosslinking diethylenetriamine molecule is 3: 1.
Example 4
This example provides a heavy metal chelating agent prepared by replacing "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 2" with "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 0.1", and the others are kept the same, obtaining the heavy metal chelating agent, which has a molecular weight range of 80000-.
Example 5
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 2" with "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 3", and the others are kept the same, obtaining the heavy metal chelating agent, and determining the molecular weight range thereof by gel chromatography (GPC) to be 10000-.
Example 6
This example provides a heavy metal chelating agent prepared by replacing "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 2" with "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 0.05", and the others are kept the same, to obtain the heavy metal chelating agent, which has a molecular weight range of 70000-140000 daltons as measured by gel chromatography (GPC).
Example 7
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 2" with "the molar ratio of 1, 2-dichloroethane to the one-sided protected diethylenetriamine is 1: 4", and the others are kept the same, obtaining the heavy metal chelating agent, and measuring the molecular weight range by gel chromatography (GPC) to be 5000-.
Example 8
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 3: 1" with "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 0.5: 1", and keeping the other conditions consistent, and the heavy metal chelating agent is obtained, and the molecular weight range is 10000-.
Example 9
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 3: 1" with "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 6: 1", and keeping the other conditions consistent, and the heavy metal chelating agent is obtained, and the molecular weight range is 30000-60000 dalton as determined by gel chromatography (GPC).
Example 10
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 3: 1" with "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 0.3: 1", and keeping the other conditions consistent, and the heavy metal chelating agent is obtained, and the molecular weight range is 5000-30000 dalton as determined by gel chromatography (GPC).
Example 11
This example provides a heavy metal chelating agent, which is prepared by replacing "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 3: 1" with "the molar ratio of carbon disulfide to deprotected crosslinked diethylenetriamine molecule is 8: 1", and keeping the other conditions consistent, and the heavy metal chelating agent is obtained, and the molecular weight range is 30000-60000 dalton as determined by gel chromatography (GPC).
Example 12
Respectively weighing 140g of the heavy metal chelating agent prepared in the embodiments 1 to 11, adding deionized water to the volume of 500mL, and preparing the heavy metal chelating agent containing 100mg/L Pb 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ni 2+ The above 11 chelating agent solutions were added in an amount of 0.06mL to 200mL each of the simulated wastewater, and the mixture was magnetically stirred for 10min, then allowed to stand for 30min, then filtered through a 0.45 μm filter membrane, and the residual amounts of heavy metals in the filtrate were measured by an atomic absorption spectrometer to calculate the removal rates of the respective heavy metals, the results of which are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the heavy metal chelating agent of the present invention, heavy metal Pb, is a heavy metal 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ni 2+ Has good effect. Comparing example 1 with examples 4-7, when the molar ratio of the chain extender to the unilateral protected polyethylene polyamine is 1 (0.1-3), the prepared heavy metal chelating agent has better heavy metal chelating effect; comparing example 1 with examples 8-11, when the molar ratio of the carbon disulfide to the deprotected crosslinked polyethylene polyamine molecule is (0.5-6):1, the obtained heavy metal chelating agent also has better heavy metal chelating effect.
The applicant states that the present invention is illustrated by the above examples to the heavy metal chelating agent of the present invention, the preparation method and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (41)
1. The preparation method of the heavy metal chelating agent is characterized by comprising the following steps:
(1) using polyene polyamine molecules as raw materials, and carrying out unilateral protection on terminal primary amine of the polyene polyamine molecules by using di-tert-butyl dicarbonate to obtain unilateral-protected polyene polyamine;
(2) carrying out chain extension crosslinking reaction on the unilateral protected polyene polyamine obtained in the step (1) and a chain extender to obtain crosslinked polyene polyamine; the molar ratio of the chain extender to the unilateral protected polyene polyamine molecule is 1 (0.1-3);
(3) removing the unilateral protection of the crosslinked polyene polyamine in the step (2) to obtain deprotected crosslinked polyene polyamine;
(4) carrying out xanthation acylation reaction on the deprotected crosslinked polyene polyamine obtained in the step (3) and carbon disulfide to obtain the heavy metal chelating agent, wherein the molar ratio of the carbon disulfide to the deprotected crosslinked polyene polyamine molecule is (0.5-6) to 1;
the polyene polyamine molecule in the step (1) is any one or the combination of at least two of ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
the chain extender of step (2) is a dihaloalkane.
2. The preparation method according to claim 1, wherein the specific method for unilateral protection of terminal primary amine of polyene polyamine molecule by di-tert-butyl dicarbonate in step (1) is as follows:
dissolving polyene polyamine molecule in alkali solution, and adding di-tert-butyl dicarbonate to make reaction.
3. The method of claim 2, wherein the base is sodium hydroxide and/or potassium hydroxide.
4. The process of claim 3, wherein the molar ratio of base to polyene polyamine molecule is 2 (0.8-15).
5. The method of claim 2, wherein the solvent of the alkali solution is deionized water.
6. The method according to claim 2, wherein the alkali solution is present in an amount of 45 to 90% by mass.
7. The process according to claim 2, wherein the molar ratio of di-tert-butyl dicarbonate to polyene polyamine molecule is (0.9-1.3): 1.
8. The method of claim 2, wherein the di-tert-butyl dicarbonate is added dropwise.
9. The method according to claim 2, wherein the di-tert-butyl dicarbonate is added while stirring.
10. The process according to claim 2, wherein the temperature at which di-tert-butyl dicarbonate is added is 0 ℃.
11. The method of claim 2, wherein the reaction temperature is 20-30 ℃.
12. The method of claim 2, wherein the reaction time is 2 to 3 hours.
13. The method of claim 1 wherein the dihaloalkane is any one of 1, 2-dichloroethane, 1, 3-dichloropropane, 1, 4-dichlorobutane or 1, 2-dibromoethane or a combination of at least two thereof.
14. The preparation method of claim 1, wherein the chain-extended crosslinking reaction of the single-side protected polyene polyamine and the chain extender in the step (2) is carried out by the following specific method:
adding a chain extender into an alkaline solution dissolved with unilateral protection polyene polyamine to carry out chain extension crosslinking reaction.
15. The method of claim 14, wherein the base is sodium hydroxide and/or potassium hydroxide.
16. The method of claim 14, wherein the solvent of the alkali solution is deionized water.
17. The method according to claim 14, wherein the alkali solution is present in an amount of 45 to 90% by mass.
18. The method of claim 14, wherein the chain extender is added dropwise.
19. The method of claim 14, wherein the chain extender is added while stirring is applied.
20. The method of claim 14, wherein the temperature at which the chain extender is added is 0 ℃.
21. The method of claim 14, wherein the reaction temperature is 20-30 ℃.
22. The method of claim 14, wherein the reaction time is 1 to 3 hours.
23. The process according to claim 1, wherein the one-sided protection by removing the crosslinked polyene polyamine in the step (3) is carried out in an acidic environment.
24. The method of claim 23, wherein the acidic environment has a pH of 3 to 4.
25. The method of claim 23, wherein the acidic environment is obtained by adding an acid solution to the reaction system.
26. The method of claim 25, wherein the acid is any one of sulfuric acid, hydrochloric acid, acetic acid, trifluoroacetic acid, or benzenesulfonic acid, or a combination of at least two thereof.
27. The method of claim 25, wherein the solvent of the acid solution is deionized water.
28. The method of claim 25, wherein the acid solution has a concentration of 1% to 60%.
29. The method according to claim 25, wherein the amount of the acid solution added is 1 (6 to 20) in terms of the mass ratio of the crosslinked polyene polyamine.
30. The method according to claim 1, wherein the deprotection temperature in the step (3) is 20 to 30 ℃.
31. The method of claim 1, wherein the deprotection time in step (3) is 4 to 6 hours.
32. The process according to claim 1, wherein the step (4) comprises xanthogenating the deprotected crosslinked polyene polyamine with carbon disulfide by:
and (4) adding an alkali solution into the reaction system obtained in the step (3), and then adding carbon disulfide for reaction.
33. The method of claim 32, wherein the base is sodium hydroxide and/or potassium hydroxide.
34. The method of claim 32, wherein the solvent of the alkaline solution is deionized water.
35. The method of claim 32, wherein the concentration of the alkali solution is 45% to 90% by mass.
36. The method of claim 32, wherein the carbon disulfide is added dropwise.
37. The method of claim 32, wherein the carbon disulfide is added while stirring.
38. The method of claim 32, wherein the reaction is carried out in two steps: firstly, reacting for 1-3h at 20-30 ℃; and reacting for 2-3h at 60-65 ℃.
39. A heavy metal chelator produced by the method of preparation of any one of claims 1 to 38.
40. Use of a heavy metal chelator according to claim 39 to precipitate heavy metals.
41. The use according to claim 40, wherein the heavy metal is a heavy metal in waste incineration fly ash.
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| 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 |
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| 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 |
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