CN109704974A - Heavy metal chelating agent and preparation method and application thereof - Google Patents

Heavy metal chelating agent and preparation method and application thereof Download PDF

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CN109704974A
CN109704974A CN201811614682.XA CN201811614682A CN109704974A CN 109704974 A CN109704974 A CN 109704974A CN 201811614682 A CN201811614682 A CN 201811614682A CN 109704974 A CN109704974 A CN 109704974A
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polyamines polyene
reaction
heavy metal
crosslinking
preparation
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CN109704974B (en
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胡清
王峰
唐一
童立志
胡滨
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Southern University of Science and Technology
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Southern University of Science and Technology
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
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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

A kind of heavy metal chelant and its preparation method and application
Technical field
The present invention relates to metal-chelator technical fields, and in particular to a kind of heavy metal chelant and preparation method thereof and answers With more particularly to a kind of high chelating ability of high reaction activity heavy metal chelant and its preparation method and application.
Background technique
Incineration of refuse flyash is a kind of Dark grey or linen fine-powder, and 90% fly ash granule partial size is less than 300 μ M, often rich in having the heavy metals such as copper, chromium, lead, zinc, cadmium, nickel, tin, manganese, mercury, arsenic and its corresponding oxide in flying dust, how The heavy metal being effectively treated in incineration of refuse flyash is that we to be paid close attention to.Chemical chelating method be a kind of effect preferably, cost Lower heavy metal flyash treatment method, moreover it is possible to the improvement suitable for extensive flying dust.Based on this, prior art discloses many The artificial synthesized high-molecular chelating agent for handling flying dust, such as dithiocarbamates chelating agent, ethylenediamine tetra-acetic acid (EDTA) chelating agent etc.;In addition there are some natural chelating agents, such as citric acid, tartaric acid, oxalic acid traditional treatment method, but It is all to expose a series of problems, such as heavy metal recovery is difficult, chelating is not thorough, effect of settling is undesirable.Study carefully its main cause also It is since chelant ties have a single function, chelating point is few, therefore the chelating formed is small in size, chelating area is small, settling property is poor And big excessive concentrations need to be maintained to can be only achieved better effects.
CN103172159A discloses a kind of preparation method of compound heavy metal chelant, includes the following steps: 1) to exist Water and polyamine compounds are added in reaction kettle and stir evenly;2) haloalkylene oxide is slowly added dropwise in a kettle and keeps temperature No more than 50 DEG C;3) reaction kettle is warming up between 50-90 DEG C, and continues to be stirred to react 2-6 hours at this temperature;4) it is reacting Lead to cooling water in kettle and be down to 25-35 DEG C, three mercaptan trisodium salt of 1.3.5- triazine -2.4.6- is then added, is within stirring 0.5-1 hours Obtain compound heavy metal chelant.Heavy metal chelant prepared by the present invention, remains the environmental-friendly advantage of TMT-15, and gram The shortcomings that having taken that its wadding body is small, having precipitated sad filter, can it is subsequent be not necessarily to another addition polymerization acrylamide flocculating agent in the case where use Water content of beary metal is lower than national standard.But the chelating agent haves the shortcomings that chelating is less, settling property is by certain Limitation.
CN108379765A discloses a kind of heavy metal chelant and preparation method thereof, and the heavy metal chelant is by good fortune beauty Sodium 10-25 parts by weight, sodium phosphate 5-15 parts by weight, EDTA 5-20 parts by weight, polycarboxylic acids 0.5-1 parts by weight and glucose 5-10 Parts by weight composition.Will above-mentioned raw materials be added softened water in, stir and evenly mix, stands 20 hours after be separated by solid-liquid separation, it is separated out liquid Body is the heavy metal chelant.Should heavy metal chelant can use at different temperatures, to pH range be 3-11 fly Ash has preferable chelate effect, and Environmental Safety is nontoxic, and product characteristics are stablized after chelating, acidity and time in correlation standard Under will not release heavy metal again.But still remain chelating point less, formed chelating it is small in size, chelating area it is small, sedimentation The disadvantages of performance is poor.
CN106955451A discloses a kind of incineration of refuse flyash heavy metal chelant, including is by weight 1:(2-3) Mixed compounding chelating agent and sodium hydroxide solution, wherein it is described compounding chelating agent include count as following weight percent at Point: organic sequestering agent: 60-90%;Inorganic chelator: 10-40%;The organic sequestering agent is dithiocarbamates, Selected from zinc diethyl dithiocarbamate, zinc dimethyl dithiocarbamate, NB sodium dibutyl dithiocarbamate or two One of benzyl nabam is a variety of;The inorganic chelator be selected from one of vulcanized sodium, sodium phosphate or Two kinds.The heavy metal chelant can reduce Leaching of Heavy Metals concentration, guarantee that flyash curing sample block meets leaching concentration limit value, But chelating point is less, the chelating of formation is small in size, chelating area is small, the heavy metal in garbage flying ash cannot be made effectively to settle.
Therefore, one kind is developed containing more chelating sites, and there is the high chelating ability of high reaction activity, can make in garbage flying ash Heavy metal to obtain the heavy metal chelant of High-rate sedimentation be meaningful.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of heavy metal chelant and preparation method thereof and Using especially providing a kind of heavy metal chelant and its preparation method and application of high chelating ability of high reaction activity.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of preparation method of heavy metal chelant, and the preparation method includes the following steps:
(1) using polyamines polyene molecule as raw material, unilateral protection is carried out to its end group primary amine with di-tert-butyl dicarbonate, is obtained The polyamines polyene of unilateral protection;
(2) polyamines polyene Yu cahin extension agent for the unilateral protection for obtaining step (1) carry out chain cross-linking reaction, are crosslinked Polyamines polyene;
(3) the unilateral protection of removing step (2) the crosslinking polyamines polyene obtains deprotection crosslinking polyamines polyene;
(4) the deprotection crosslinking polyamines polyene and carbon disulfide obtained step (3) carries out xanthan acylation reaction, obtains institute State heavy metal chelant.
The preparation method of heavy metal chelant of the present invention is first by a part of amino on polyamines polyene strand It is protected with di-tert-butyl dicarbonate, it is made to be not involved in subsequent cross-linking reaction, after the completion of cross-linking reaction, then remove amino Protection, so that final crosslinking polyamines polyene is possessed the more reaction site with carbon disulfide, also just possess a more huge sum of moneys Belong to chelating site, so that chelating ability greatly improves.
In the present invention, step (1) the polyamines polyene molecule include ethylenediamine, diethylenetriamine, triethylene tetramine or In tetraethylenepentamine any one or at least two combination, described two combinations include ethylenediamine and diethylenetriamine, Diethylenetriamine and triethylene tetramine, triethylene tetramine and tetraethylenepentamine etc..
Preferably, step (1) is described carries out unilateral guarantor with end group primary amine of the di-tert-butyl dicarbonate to polyamines polyene molecule Shield method particularly includes:
By polyamines polyene molecular melting in aqueous slkali, and di-tert-butyl dicarbonate is added thereto and is reacted.
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide.
Preferably, the molar ratio of the alkali and polyamines polyene molecule is 2:(0.8-15), such as 2:0.8,2:1,2:3,2: 5,2:8,2:10,2:12 or 2:15 etc..
Preferably, the solvent of the aqueous slkali is deionized water.
Preferably, the mass percentage concentration of the aqueous slkali be 45%-90%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% etc..
Preferably, the molar ratio of the di-tert-butyl dicarbonate and polyamines polyene 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 etc..
Preferably, the mode that di-tert-butyl dicarbonate is added is to be added dropwise.
Preferably, it gives and stirs while the addition di-tert-butyl dicarbonate.
Preferably, the temperature when addition di-tert-butyl dicarbonate is 0 DEG C.
Preferably, the temperature of the reaction 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 time of the reaction be 2-3h, such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 3h etc..
In the present invention, step (2) described cahin extension agent includes saturated dihalide and/or haloalkylene oxide.
Preferably, the saturated dihalide includes 1,2- dichloroethanes, 1,3- dichloropropane, Isosorbide-5-Nitrae-dichloroetane or 1,2- bis- In bromoethane any one or at least two combination, described two combinations such as 1,2- dichloroethanes and 1,3- dichloro third Alkane, 1,3- dichloropropane and 1,4- dichloroetane, 1,4- dichloroetane and glycol dibromide etc..
Preferably, the haloalkylene oxide includes chloro alkylene oxide and/or Brominated Epoxy alkane.
Preferably, the molar ratio of step (2) cahin extension agent and the polyamines polyene molecule of unilateral protection 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 specific selection of the molar ratio of the polyamines polyene molecule of the cahin extension agent and unilateral protection is in 1:(0.1-3) range, It is because being more than that this range can generate sedimentation, while branched chain type product increases, so that steric hindrance increase, chela when chelating heavy metal Close degradation;It can be reacted not exclusively less than this range, crosslinking is not thorough, and the molecular weight of the chelating agent of formation is less than normal, precipitating weight The performance of metal is poor.
Preferably, the polyamines polyene Yu cahin extension agent of step (2) the unilateral protection carry out the specific side of chain cross-linking reaction Method are as follows:
Cahin extension agent is added in the aqueous slkali dissolved with unilateral protection polyamines polyene, chain cross-linking reaction is carried out.
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide.
Preferably, the solvent of the aqueous slkali is deionized water.
Preferably, the mass percentage concentration of the aqueous slkali be 45%-90%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% etc..
Preferably, the mode that cahin extension agent is added is to be added dropwise.
Preferably, it gives and stirs while the addition cahin extension agent.
Preferably, the temperature when addition cahin extension agent is 0 DEG C.
Preferably, the temperature of the reaction 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 time of the reaction be 1-3h, such as 1h, 1.2h, 1.5h, 1.7h, 2h, 2.2h, 2.5h, 2.6h, 2.8h or 3h etc..
In the present invention, the unilateral protection of step (3) the removing crosslinking polyamines polyene is carried out in acidic environment.
Preferably, the pH value of the acidic environment is 3-4, such as 3,3.2,3.4,3.6,3.8 or 4 etc..
Preferably, the acidic environment is by being added what acid solution obtained in the reaction system.
Preferably, the acid includes any one in sulfuric acid, hydrochloric acid, acetic acid, trifluoroacetic acid or benzene sulfonic acid or at least two Kind combination, described two combinations such as sulfuric acid and hydrochloric acid, hydrochloric acid and acetic acid, trifluoroacetic acid and benzene sulfonic acid etc..
Preferably, the solvent of the acid solution is deionized water.
Preferably, the concentration of the acid solution be 1%-60%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50% or 60% etc..
Preferably, the mass ratio of the additional amount of the acid solution and crosslinking polyamines polyene is 1:(6-20), such as 1:6,1: 8,1:10,1:12,1:14,1:16,1:17,1:18,1:19 or 1:20 etc..
Preferably, the temperature of step (3) described deprotection be 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 time of step (3) described deprotection be 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 present invention, step (4) the deprotection crosslinking polyamines polyene and carbon disulfide carry out xanthan acylation reaction Method particularly includes:
Aqueous slkali is added in the reaction system obtained to step (3), adds carbon disulfide and is reacted.
Preferably, the molar ratio of the carbon disulfide and deprotection crosslinking polyamines polyene 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 etc..
The specific selection of molar ratio of the carbon disulfide and deprotection crosslinking polyamines polyene is at (0.5-6): 1 range is Because being more than that this range can make the carbon disulfide for having neither part nor lot in reaction sink to solution bottom, gradually volatilize in subsequent use process, Atmosphere pollution is caused, operator's health and environment are adversely affected;The product of synthesis can be made water-soluble less than this range Property be deteriorated even it is fairly insoluble, thus cause chelating heavy metal failure.
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide.
Preferably, the solvent of the aqueous slkali is deionized water.
Preferably, the mass percentage concentration of the aqueous slkali be 45%-90%, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% etc..
Preferably, the mode that carbon disulfide is added is to be added dropwise.
Preferably, it gives and stirs while the addition carbon disulfide.
Preferably, it is described reaction be carried out in two steps: first 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.) under react 1-3h (such as 1h, 1.2h, 1.5h, 1.7h, 2h, 2.2h, 2.5h, 2.6h, 2.8h or 3h etc.);2-3h is reacted under 60-65 DEG C (60 DEG C, 61 DEG C, 62 DEG C, 63 DEG C, 64 DEG C or 65 DEG C etc.) again (such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 3h etc.).
As the preferred technical solution of the present invention, the preparation method includes the following steps:
(1) using polyamines polyene molecule as raw material, unilateral protection is carried out to its end group primary amine with di-tert-butyl dicarbonate, wherein The molar ratio of di-tert-butyl dicarbonate and polyamines polyene molecule is (0.9-1.3): 1, reaction carries out 2-3h at 20-30 DEG C, obtains To the polyamines polyene of unilateral protection;
(2) under alkaline condition, the polyamines polyene and cahin extension agent of unilateral protection step (1) obtained carry out chain crosslinking Reaction, wherein the molar ratio of the polyamines polyene molecule of cahin extension agent and unilateral protection is 1:(0.1-3), reaction at 20-30 DEG C into Row 1-3h obtains crosslinking polyamines polyene;
(3) in acid condition, the unilateral protection of removing step (2) the crosslinking polyamines polyene, reacts at 20-30 DEG C 4-6h is carried out, deprotection crosslinking polyamines polyene is obtained;
(4) under alkaline condition, the deprotection crosslinking polyamines polyene and carbon disulfide step (3) obtained carries out xanthyl Change reaction, wherein the molar ratio of carbon disulfide and deprotection crosslinking polyamines polyene molecule is (0.5-6): 1, it reacts at 20-30 DEG C Lower reaction 1-3h, then 2-3h is reacted at 60-65 DEG C, obtain the heavy metal chelant.
Second aspect, the present invention provide a kind of heavy metal chelant being prepared by preparation method as described above.
The third aspect, the present invention provide a kind of application of heavy metal chelant as described above in precipitation of heavy metals.
Preferably, the heavy metal is the heavy metal in incineration of refuse flyash.
Compared with the existing technology, the invention has the following advantages:
The preparation method strong operability of heavy metal chelant of the present invention, simple process, and the chela being prepared Mixture contains more chelating site, has high reaction activity and high chelating ability, heavy metal can be made efficiently to be precipitated, 82.8%-99.3% is up to the removal rate of heavy metal.
Specific embodiment
Further to illustrate technological means and its effect adopted by the present invention, below in conjunction with preferred implementation of the invention Example to further illustrate the technical scheme of the present invention, but the present invention is not limited in scope of embodiments.
Embodiment 1
The present embodiment provides a kind of heavy metal chelant, preparation method includes the following steps:
(1) at 0 DEG C, diethylenetriamine and solid sodium hydroxide is dissolved in deionized water, is vigorously stirred down and passes through Di-tert-butyl dicarbonate is slowly added dropwise in addition funnel thereto, and 25 DEG C of reaction 3h are restored to after being added dropwise, obtain unilateral protection Diethylenetriamine;
(2) above-mentioned reaction system is cooled to 0 DEG C with ice-water bath again, then with vigorous stirring by addition funnel to 1,2- dichloroethanes is wherein slowly added dropwise, control rate of addition about 6s mono- drips, 25 DEG C of reaction 2h are restored to after being added dropwise, are obtained It is crosslinked diethylenetriamine;The molar ratio of the 1,2- dichloroethanes and the diethylenetriamine of unilateral protection is 1:2;
(3) 6N HCl solution is slowly added dropwise in Xiang Shangshu reaction system, until system pH reaches 4,25 DEG C after being added dropwise Lower reaction 5h obtains deprotection crosslinking diethylenetriamine;
(4) Xiang Shangshu reaction system be added dropwise saturation NaOH aqueous solution, then with vigorous stirring by addition funnel to its In be slowly added dropwise carbon disulfide, control rate of addition 4s mono- drips, and reacts 2h at 25 DEG C after being added dropwise, then loads onto reflux condensation mode Pipe carries out oil bath and heats reaction 2h at 65 DEG C up to the heavy metal chelant, measures its molecule with exclusion chromatography (GPC) Amount range is 20000-50000 dalton;The molar ratio of the carbon disulfide and deprotection crosslinking diethylenetriamine molecule is 3: 1。
Embodiment 2
The present embodiment provides a kind of heavy metal chelant, preparation method includes the following steps:
(1) at 0 DEG C, triethylene tetramine and solid potassium hydroxide is dissolved in deionized water, is vigorously stirred down and passes through Di-tert-butyl dicarbonate is slowly added dropwise in addition funnel thereto, and 20 DEG C of reaction 3h are restored to after being added dropwise, obtain unilateral protection Triethylene tetramine;
(2) above-mentioned reaction system is cooled to 0 DEG C with ice-water bath again, then with vigorous stirring by addition funnel to 1,3- dichloropropane is wherein slowly added dropwise, control rate of addition about 5s mono- drips, 30 DEG C of reaction 1h are restored to after being added dropwise, are obtained It is crosslinked triethylene tetramine;The molar ratio of the 1,3- dichloropropane and the triethylene tetramine of unilateral protection is 1:2;
(3) 6N acetic acid solution is slowly added dropwise in Xiang Shangshu reaction system, until system pH reaches 3,30 DEG C after being added dropwise Lower reaction 4h obtains deprotection crosslinking triethylene tetramine;
(4) saturation KOH aqueous solution is added dropwise in Xiang Shangshu reaction system, then passes through addition funnel thereto with vigorous stirring Carbon disulfide is slowly added dropwise, control rate of addition 4s mono- drips, reacts 1h at 30 DEG C after being added dropwise, then load onto reflux condensation mode Pipe carries out oil bath and heats reaction 3h at 60 DEG C up to the heavy metal chelant, measures its molecule with exclusion chromatography (GPC) Amount range is 40000-70000 dalton;The molar ratio of the carbon disulfide and deprotection crosslinking triethylene tetramine molecule is 3: 1。
Embodiment 3
The present embodiment provides a kind of heavy metal chelant, preparation method includes the following steps:
(1) at 0 DEG C, diethylenetriamine and solid sodium hydroxide is dissolved in deionized water, is vigorously stirred down and passes through Di-tert-butyl dicarbonate is slowly added dropwise in addition funnel thereto, and 30 DEG C of reaction 2h are restored to after being added dropwise, obtain unilateral protection Diethylenetriamine;
(2) above-mentioned reaction system is cooled to 0 DEG C with ice-water bath again, then with vigorous stirring by addition funnel to Isosorbide-5-Nitrae-dichloroetane is wherein slowly added dropwise, control rate of addition about 5s mono- drips, 20 DEG C of reaction 3h are restored to after being added dropwise, are obtained It is crosslinked diethylenetriamine;The molar ratio of the 1,4- dichloroetane and the diethylenetriamine of unilateral protection is 1:2;
(3) 6N HCl solution is slowly added dropwise in Xiang Shangshu reaction system, until system pH reaches 3.5,20 after being added dropwise 6h is reacted at DEG C, obtains deprotection crosslinking diethylenetriamine;
(4) Xiang Shangshu reaction system be added dropwise saturation NaOH aqueous solution, then with vigorous stirring by addition funnel to its In be slowly added dropwise carbon disulfide, control rate of addition 4s mono- drips, and reacts 3h at 20 DEG C after being added dropwise, then loads onto reflux condensation mode Pipe carries out oil bath and heats reaction 3h at 60 DEG C up to the heavy metal chelant, measures its molecule with exclusion chromatography (GPC) Amount range is 20000-50000 dalton;The molar ratio of the carbon disulfide and deprotection crosslinking diethylenetriamine molecule is 3: 1。
Embodiment 4
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 be only that by " described 1, The molar ratio of 2- dichloroethanes and the diethylenetriamine of unilateral protection is that 1:2 " is substituted for " the 1,2- dichloroethanes and unilateral guarantor The molar ratio of the diethylenetriamine of shield is 1:0.1 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 80000-120000 dalton.
Embodiment 5
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 be only that by " described 1, The molar ratio of 2- dichloroethanes and the diethylenetriamine of unilateral protection is that 1:2 " is substituted for " the 1,2- dichloroethanes and unilateral guarantor The molar ratio of the diethylenetriamine of shield is 1:3 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 10000-40000 dalton.
Embodiment 6
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 be only that by " described 1, The molar ratio of 2- dichloroethanes and the diethylenetriamine of unilateral protection is that 1:2 " is substituted for " the 1,2- dichloroethanes and unilateral guarantor The molar ratio of the diethylenetriamine of shield is 1:0.05 ", other are consistent, and obtain the heavy metal chelant, use gel chromatography It is 70000-140000 dalton that method (GPC), which measures its molecular weight ranges,.
Embodiment 7
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 be only that by " described 1, The molar ratio of 2- dichloroethanes and the diethylenetriamine of unilateral protection is that 1:2 " is substituted for " the 1,2- dichloroethanes and unilateral guarantor The molar ratio of the diethylenetriamine of shield is 1:4 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 5000-30000 dalton.
Embodiment 8
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 is only that " described two Nitric sulfid and the molar ratio for being deprotected crosslinking diethylenetriamine molecule are that 3:1 " is substituted for " carbon disulfide and deprotection crosslinking The molar ratio of diethylenetriamine molecule is 0.5:1 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 10000-40000 dalton.
Embodiment 9
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 is only that " described two Nitric sulfid and the molar ratio for being deprotected crosslinking diethylenetriamine molecule are that 3:1 " is substituted for " carbon disulfide and deprotection crosslinking The molar ratio of diethylenetriamine molecule is 6:1 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 30000-60000 dalton.
Embodiment 10
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 is only that " described two Nitric sulfid and the molar ratio for being deprotected crosslinking diethylenetriamine molecule are that 3:1 " is substituted for " carbon disulfide and deprotection crosslinking The molar ratio of diethylenetriamine molecule is 0.3:1 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 5000-30000 dalton.
Embodiment 11
The present embodiment provides a kind of heavy metal chelant, the difference of preparation method and embodiment 1 is only that " described two Nitric sulfid and the molar ratio for being deprotected crosslinking diethylenetriamine molecule are that 3:1 " is substituted for " carbon disulfide and deprotection crosslinking The molar ratio of diethylenetriamine molecule is 8:1 ", other are consistent, and obtain the heavy metal chelant, use exclusion chromatography (GPC) measuring its molecular weight ranges is 30000-60000 dalton.
Embodiment 12
Heavy metal chelant 140g made from embodiment 1-11 is weighed respectively and is settled to 500mL with deionized water, and is prepared Contain 100mg/L Pb respectively2+、Zn2+、Cu2+、Cd2+、Ni2+Each 200mL of simulated wastewater, be separately added on 0.06mL thereto 11 kinds of chelating agent solutions are stated, with standing 30min after magnetic agitation 10min, then with 0.45 μm of membrane filtration, are surveyed with atomic absorption instrument The residual quantity for determining heavy metal in filtrate calculates the removal rate of each heavy metal, and the results are shown in Table 1.
Table 1
From the data in table 1, it can be seen that heavy metal chelant heavy metal Pb of the present invention2+、Zn2+、Cu2+、Cd2+、Ni2+Have Good effect.Comparative example 1 and embodiment 4-7, when the molar ratio of cahin extension agent and the polyethylene polyamine of unilateral protection is 1: When (0.1-3), heavy metal chelant obtained has better heavy metal chelating effect;Comparative example 1 and embodiment 8-11, When the molar ratio of carbon disulfide and deprotection crosslinking polyethylene polyamine molecule is (0.5-6): when 1, heavy metal chelant obtained Also there is better heavy metal chelating effect.
The Applicant declares that the present invention is explained by the above embodiments heavy metal chelant and preparation method thereof of the invention And application, but the present invention is not limited to the above embodiments, that is, it is real not mean that the present invention must rely on above-described embodiment ability It applies.It should be clear to those skilled in the art, any improvement in the present invention, to the equivalent of each raw material of product of the present invention Replacement and addition, the selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

Claims (10)

1. a kind of preparation method of heavy metal chelant, which is characterized in that the preparation method includes the following steps:
(1) using polyamines polyene molecule as raw material, unilateral protection is carried out to its end group primary amine with di-tert-butyl dicarbonate, is obtained unilateral The polyamines polyene of protection;
(2) polyamines polyene Yu cahin extension agent for the unilateral protection for obtaining step (1) carry out chain cross-linking reaction, obtain crosslinking polyenoid Polyamines;
(3) the unilateral protection of removing step (2) the crosslinking polyamines polyene obtains deprotection crosslinking polyamines polyene;
(4) the deprotection crosslinking polyamines polyene and carbon disulfide obtained step (3) carries out xanthan acylation reaction, obtains described heavy Metal-chelator.
2. preparation method as described in claim 1, which is characterized in that step (1) the polyamines polyene molecule include ethylenediamine, In diethylenetriamine, triethylene tetramine or tetraethylenepentamine any one or at least two combination.
3. preparation method as claimed in claim 1 or 2, which is characterized in that step (1) it is described with di-tert-butyl dicarbonate to more The end group primary amine of alkene polyamine molecule carries out unilateral protection method particularly includes:
By polyamines polyene molecular melting in aqueous slkali, and di-tert-butyl dicarbonate is added thereto and is reacted;
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide;
Preferably, the molar ratio of the alkali and polyamines polyene molecule is 2:(0.8-15);
Preferably, the solvent of the aqueous slkali is deionized water;
Preferably, the mass percentage concentration of the aqueous slkali is 45%-90%;
Preferably, the molar ratio of the di-tert-butyl dicarbonate and polyamines polyene molecule is (0.9-1.3): 1;
Preferably, the mode that di-tert-butyl dicarbonate is added is to be added dropwise;
Preferably, it gives and stirs while the addition di-tert-butyl dicarbonate;
Preferably, the temperature when addition di-tert-butyl dicarbonate is 0 DEG C;
Preferably, the temperature of the reaction is 20-30 DEG C;
Preferably, the time of the reaction is 2-3h.
4. preparation method as claimed in any one of claims 1-3, which is characterized in that step (2) cahin extension agent includes two Alkyl halide and/or haloalkylene oxide;
Preferably, the saturated dihalide includes 1,2- dichloroethanes, 1,3- dichloropropane, Isosorbide-5-Nitrae-dichloroetane or 1,2- dibromo second In alkane any one or at least two combination;
Preferably, the haloalkylene oxide includes chloro alkylene oxide and/or Brominated Epoxy alkane;
Preferably, the molar ratio of step (2) cahin extension agent and the polyamines polyene molecule of unilateral protection is 1:(0.1-3).
5. such as preparation method of any of claims 1-4, which is characterized in that step (2) the unilateral protection it is more Alkene polyamines and cahin extension agent carry out chain cross-linking reaction method particularly includes:
Cahin extension agent is added in the aqueous slkali dissolved with unilateral protection polyamines polyene, chain cross-linking reaction is carried out;
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide;
Preferably, the solvent of the aqueous slkali is deionized water;
Preferably, the mass percentage concentration of the aqueous slkali is 45%-90%;
Preferably, the mode that cahin extension agent is added is to be added dropwise;
Preferably, it gives and stirs while the addition cahin extension agent;
Preferably, the temperature when addition cahin extension agent is 0 DEG C;
Preferably, the temperature of the reaction is 20-30 DEG C;
Preferably, the time of the reaction is 1-3h.
6. preparation method according to any one of claims 1 to 5, which is characterized in that step (3) removing is crosslinked polyenoid The unilateral protection of polyamines is carried out in acidic environment;
Preferably, the pH value of the acidic environment is 3-4;
Preferably, the acidic environment is by being added what acid solution obtained in the reaction system;
Preferably, the acid includes any one in sulfuric acid, hydrochloric acid, acetic acid, trifluoroacetic acid or benzene sulfonic acid or at least two Combination;
Preferably, the solvent of the acid solution is deionized water;
Preferably, the concentration of the acid solution is 1%-60%;
Preferably, the mass ratio of the additional amount of the acid solution and crosslinking polyamines polyene is 1:(6-20);
Preferably, the temperature of step (3) described deprotection is 20-30 DEG C;
Preferably, the time of step (3) described deprotection is 4-6h.
7. such as preparation method of any of claims 1-6, which is characterized in that step (4) the deprotection crosslinking is more Alkene polyamines and carbon disulfide carry out xanthan acylation reaction method particularly includes:
Aqueous slkali is added in the reaction system obtained to step (3), adds carbon disulfide and is reacted;
Preferably, the molar ratio of the carbon disulfide and deprotection crosslinking polyamines polyene molecule is (0.5-6): 1;
Preferably, the alkali includes sodium hydroxide and/or potassium hydroxide;
Preferably, the solvent of the aqueous slkali is deionized water;
Preferably, the mass percentage concentration of the aqueous slkali is 45%-90%;
Preferably, the mode that carbon disulfide is added is to be added dropwise;
Preferably, it gives and stirs while the addition carbon disulfide;
Preferably, the reaction is carried out in two steps: reacting 1-3h at 20-30 DEG C first;2-3h is reacted at 60-65 DEG C again.
8. such as preparation method of any of claims 1-7, which is characterized in that the preparation method includes following step It is rapid:
(1) using polyamines polyene molecule as raw material, unilateral protection is carried out to its end group primary amine with di-tert-butyl dicarbonate, wherein two carbon The molar ratio of sour di tert butyl carbonate and polyamines polyene molecule is (0.9-1.3): 1, reaction carries out 2-3h at 20-30 DEG C, obtains list The polyamines polyene of side protection;
(2) under alkaline condition, it is anti-that the polyamines polyene and cahin extension agent of unilateral protection step (1) obtained carry out chain crosslinking Answer, wherein the molar ratio of cahin extension agent and the polyamines polyene molecule of unilateral protection is 1:(0.1-3), reaction carries out at 20-30 DEG C 1-3h obtains crosslinking polyamines polyene;
(3) in acid condition, the unilateral protection of removing step (2) the crosslinking polyamines polyene, reaction carry out at 20-30 DEG C 4-6h obtains deprotection crosslinking polyamines polyene;
(4) under alkaline condition, it is acylated anti-that the deprotection crosslinking polyamines polyene and carbon disulfide step (3) obtained carries out xanthan It answers, wherein the molar ratio of carbon disulfide and deprotection crosslinking polyamines polyene molecule is (0.5-6): 1, reaction is anti-at 20-30 DEG C 1-3h is answered, then reacts 2-3h at 60-65 DEG C, obtains the heavy metal chelant.
9. a kind of heavy metal chelant being prepared as the preparation method as described in any one of claim 1-8.
10. application of the heavy metal chelant as claimed in claim 9 in precipitation of heavy metals;
Preferably, the heavy metal is the heavy metal in incineration of refuse flyash.
CN201811614682.XA 2018-12-27 2018-12-27 Heavy metal chelating agent and preparation method and application thereof Expired - Fee Related CN109704974B (en)

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Publication number Priority date Publication date Assignee Title
CN112169245A (en) * 2020-09-27 2021-01-05 湖南工业大学 Chelating agent for treating medical waste incineration fly ash and preparation method thereof
CN112972975A (en) * 2019-12-13 2021-06-18 浙江沣蓝环保技术有限公司 Heavy metal chelating agent and preparation method thereof
CN114378108A (en) * 2022-03-24 2022-04-22 神美科技有限公司 Heavy metal chelating agent and application thereof in removing heavy metals in household garbage

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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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Publication number Priority date Publication date Assignee Title
CN101314492A (en) * 2007-05-29 2008-12-03 陈德琪 Method for preparing novel remover for heavy metal ion and application thereof
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112972975A (en) * 2019-12-13 2021-06-18 浙江沣蓝环保技术有限公司 Heavy metal chelating agent and preparation method thereof
CN112169245A (en) * 2020-09-27 2021-01-05 湖南工业大学 Chelating agent for treating medical waste incineration fly ash and preparation method thereof
CN114378108A (en) * 2022-03-24 2022-04-22 神美科技有限公司 Heavy metal chelating agent and application thereof in removing heavy metals in household garbage
CN114378108B (en) * 2022-03-24 2022-07-22 神美科技有限公司 Heavy metal chelating agent and application thereof in removing heavy metals in household garbage

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