CN107890856A - Ultrafast sedimentation type molecule brush configuration heavy metal chelating agent and preparation method thereof and its application - Google Patents

Ultrafast sedimentation type molecule brush configuration heavy metal chelating agent and preparation method thereof and its application Download PDF

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CN107890856A
CN107890856A CN201711127098.7A CN201711127098A CN107890856A CN 107890856 A CN107890856 A CN 107890856A CN 201711127098 A CN201711127098 A CN 201711127098A CN 107890856 A CN107890856 A CN 107890856A
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phemaa
poly
heavy metal
grafting
hydroxyethyl acrylamide
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CN107890856B (en
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刘锋
唐秋实
陈燕舞
彭琦
洪丹
张浥琨
郭志杰
霍应鹏
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Handan Guanxin Technology Co., Ltd
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Shunde Vocational and Technical College
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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Abstract

The present invention relates to a kind of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent and preparation method thereof and its application, feature is the poly-hydroxyethyl acrylamide by main polymer chain, the carboxylic poly- N vinyl formamides in functional polymer side chain precursor polymer end, water, catalyst is N HOSu NHSs, 1 ethyl 3 (3 dimethylamino-propyl) carbodiimide iodomethane salt, potassium hydroxide, 1, 2 1,2-diaminocyclohexane tetraacetic acid dianhydrides and carbon disulfide prepare ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, and ultrafast sedimentation type molecule brush configuration heavy metal chelating agent is used to handle and electroplated, smelt, mining, ore dressing, waste water caused by the industry such as chemical industry and machinery.Its new chelating functional group can adsorb solvay-type heavy metal ion, each base unit can provide hexa-coordinate atom and carry out strength chelating absorption, further reacted by helping the nabam of sedimentation side chain and helping sedimentation agent that chemical precipitation occurs, big aggregation is generated within the several seconds, so as to realize rapid subsidence, there is efficient seizure and settling property.

Description

Ultrafast sedimentation type molecule brush configuration heavy metal chelating agent and preparation method thereof and its application
Technical field
The invention belongs to water technology and polymer-function material field, and in particular to a kind of ultrafast sedimentation type molecular brush Structure heavy metal chelating agent and preparation method thereof and its application, mainly for the treatment of plating, smelting, mining, ore dressing, chemical industry and machine Waste water caused by the industries such as tool.
Background technology
Heavy metal wastewater thereby is mainly derived from the industries such as plating, smelting, mining, ore dressing, chemical industry and machinery.It is useless containing heavy metal After water is discharged into natural water body, not only aquatile is constituted a threat to, and organism may be constantly enriched in by food chain It is interior, finally jeopardize the health of the mankind.Heavy metal containing wastewater treatment conventional method mainly includes chemical precipitation method, heavy metal chelating agent The precipitation method, ion-exchange, active carbon adsorption etc..Compared to ion-exchange and active carbon adsorption, heavy metal chelating agent The precipitation method have that equipment investment is few, handle high efficiency and the advantages such as cost is low, are widely used in heavy metal containing wastewater treatment industry.Mesh Before, mainly there is dithiocarbamate salt derivative using more heavy metal chelating agent in practical study（DTC classes）.
But in electroplating industry, heavy metal exists no longer in the form of single heavy metal ion, but with EDTA, winestone Acid, citric acid, NH3Stable complex compound is formed Deng material, therefore goes removing heavy metals difficulty bigger, common heavy metal chelating agent The precipitation method are difficult to obtain satisfied treatment effect.At present, the nickeliferous solvay-type electroplating wastewater of electroplating industry is most difficult to handle, it is difficult to logical Overregulate heavy metal chelating agent prescription and handling process reaches plating pollutant emission standard table 3 and requires that nickel content is less than 0.1 mg/L.Nickel waste water has turned into electroplating industry processing problem, is badly in need of development of new heavy metal chelating agent, meets industry requirement.
In recent years, novel heavy metal agent for capturing turns into study hotspot, Publication No. CN 106986432A, entitled " a kind of polymer of polyethylenediamine tetrem acid unit ", there is preferable heavy metal chelating ability, can be widely applied to various Heavy metal wastewater thereby industry and soil remediation；But novel heavy metal agent for capturing prepared by the patent application is also deposited some technologies and lacked Fall into：（1）Most of solvay-type electroplating wastewaters are acid waste water, it is impossible to which directly addition uses, and need to adjust pH value to neutrality and arrive alkalescence Effectively sedimentation could occur；（2）In the basic conditions, the novel heavy metal agent for capturing rate of charge difficulty control problem, feed intake excess It is also easy to produce and precipitates slowly or do not precipitate anti-dissolution phenomena；（3）The novel heavy metal agent for capturing sequestering power is general, each of which blocking 3 coordination atoms participation chelatropic reactions can only be provided by learning structure, ineffective to height solvay-type heavy metal containing wastewater treatment.
In a word, the rate of settling of existing heavy metal chelating agent would generally be by the factor shadow such as functional group, rate of charge, pH Ring.Rate of charge is difficult to control, and feeding intake excessive easily causes that the rate of settling is slow, and feeding intake, it is incomplete to easily cause heavy metal precipitation less.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art and provides a kind of ultrafast sedimentation type molecule brush configuration heavy metal Agent for capturing and preparation method thereof and its application, network can be adsorbed by the new chelating functional group that the polymer molecule brush of synthesis is grafted Mould assembly heavy metal ion, each base unit can provide hexa-coordinate atom and carry out strength chelating absorption, further pass through polymer Helping the nabam of sedimentation side chain and helping sedimentation agent that chemical precipitation occurs for molecular brush grafting is reacted, raw within the several seconds Into big aggregation, so as to realize rapid subsidence, there is efficient seizure and settling property.
In order to achieve the above object, the technical scheme of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent of the invention is It is achieved in that, it is characterised in that the poly-hydroxyethyl acrylamide including 1~10 part of main polymer chain（PHEMAA）, 1~80 The carboxylic polyvinylformamide in functional polymer side chain precursor polymer end of part（PNVF-COOH）, 100~ 500 parts of water, 1~5 part of catalyst are n-hydroxysuccinimide (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino Propyl group) carbodiimide iodomethane salt (EDCCH3I), 1~10 part of potassium hydroxide, 1~80 part of 1,2- cyclohexanediamine tetrems Acid dianhydride (CDTAD) and 1~10 part of carbon disulfide；It is mass fraction above.
In the technical program, the poly-hydroxyethyl acrylamide of the main polymer chain（PHEMAA）It is by common free Base polymerize or controllable living polymerization synthesis PHEMAA main polymer chains；The functional polymer side chain precursor polymer end Carboxylic polyvinylformamide（PNVF-COOH）Mainly use azo dicyano valeric acid as initiator, by it is common from The carboxylic polyvinylformamide in end is synthesized by base（PNVF-COOH）Polymer；The 1,2- cyclohexanediamine four The synthetic method of acetic acid dianhydride (CDTAD) is that 1~80 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids and 1~80 part of acetic anhydride is molten Solution is controlled in 50~70 DEG C in 1~80 part of 2- picolines, reacts 20~40 hours, obtains 1,2- cyclohexanediamine tetrems Acid dianhydride；It is mass fraction above.
In order to achieve the above object, the preparation method of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent of the invention Technical scheme, which is achieved in that, is characterized in that step is as follows：
Step 1 prepares poly-hydroxyethyl acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF)
By the poly-hydroxyethyl acrylamide of 1~10 part of main polymer chain（PHEMAA）With 1~80 part of functional polymer side chain The carboxylic polyvinylformamide in precursor polymer end（PNVF-COOH）Mixing is dissolved in 100~500 parts of water, The catalyst for adding 1~5 part is the 1- ethyls -3- (3- dimethylamino-propyls) of n-hydroxysuccinimide (NHS) and 1~5 part Carbodiimide iodomethane salt (EDCCH3I), temperature control carries out esterification 10~70 hours in 50~80 DEG C, obtains poly- hydroxyl second Base acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF)；
Step 2 prepares poly-hydroxyethyl acrylamide-grafting-polyvinylamine（PHEMAA-PVA)
Add in poly-hydroxyethyl acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF) obtained by step 1 Entering 1~10 part of potassium hydroxide, in 50~80 DEG C reaction is hydrolyzed 12~48 hours in temperature control, acquisition poly-hydroxyethyl acrylamide- Grafting-polyvinylamine（PHEMAA-PVA)；
Step 3 prepares poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyethylene Amine）(PHEMAA-g-(PVACDTANa-r-PVA))
Poly-hydroxyethyl acrylamide-grafting-polyvinylamine obtained by step 2（PHEMAA-PVA 1~80 part is added in) CDTA dianhydride (CDTAD), carries out acylation reaction 5~24 hours, and acylation degree scope control is 80~ 99%, obtain poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyvinylamine） (PHEMAA-g-(PVACDTANa-r-PVA))；
Step 4 prepares the poly-hydroxyethyl acrylamide-grafting-of Water-soluble Polymer Molecules brush（Polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyethylene amido nabam）(PHEMAA-g-( PVACDTANa-r-PVACS2Na))
Poly-hydroxyethyl acrylamide-grafting-obtained by step 3（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-poly- Vinylamine）1~10 part of carbon disulfide is added in (PHEMAA-g- (PVACDTANa-r-PVA)), temperature control enters in 20~40 DEG C Row addition reaction 1~3 hour, it is final to obtain the poly-hydroxyethyl acrylamide-grafting-of Water-soluble Polymer Molecules brush（Polyvinylamine Basic ring hexamethylene tetraacetic acid sodium-random-polyethylene amido nabam）(PHEMAA-g-( PVACDTANa-r- PVACS2Na it is)) ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, is mass fraction above.
In the technical program, the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization on 1~1000, the function The polymer side chain precursor polymer PNVF-COOH degree of polymerization is 10~200, chelating type polymer side chain PVACDTANa's Grafting rate 5~80% and help sedimentation polymer side chain PVACS2Na grafting rate is 1~5%.
In order to achieve the above object, the technology of the application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent of the invention Scheme be achieved in that be characterized in that by 0.1~1 part of water-soluble poly hydroxyethyl acrylamide-grafting-（Polyethylene Amido 1,2-diaminocyclohexane tetraacetic acid sodium-random-polyethylene amido nabam）(PHEMAA-g-(PVACDTANa-r- PVACS2Na)) it is added in 100~1000 parts of waste water, is stirred 1~5 minute under normal temperature, adjusts pH to 1~14, weighed in waste water Metal ion and polymer molecule brush (PHEMAA-g- (PVACDTANa-r-PVACS2Na chelating type side chain PVACDTANa)) Generation chelating absorption, 0.01~0.1 part of the sedimentation agent that helps is added, is stirred 1 minute under normal temperature, helps the metal ion of sedimentation agent will Quickly with Water-soluble Polymer Molecules brush (PHEMAA-g- (PVACDTANa-r-PVACS2Na sedimentation side chain is helped on)) PVACS2Chemical precipitation reaction occurs for Na, and flco of the particle diameter more than 500 μm is generated in 5 seconds and is precipitated, can quickly realize removal waste water In solvay-type heavy metal ion, be mass fraction above.
It is described to help sedimentation agent as calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, alchlor in the technical program One or more kinds of any combination.
The present invention compared with prior art, has the following advantages and effect：
1st, solve prior art heavy metal chelating agent rate of settling difficulty control technology problem, optimize and set from molecular level Meter, by introducing new chelating functional group and nabam functional group, there is efficient seizure and settling property, Help under the synergy of sedimentation agent, big sedimentation aggregation can be generated within the several seconds.The rate of settling is not by the when pH value of feeding intake Influence, rapid subsidence is realized in the range of wider pH1~14；
2nd, due to introducing new chelating type functional group, Absorptive complex wave can occur to solvay-type heavy metal ion, solves work The DTC classes agent for capturing that industry uses catches the bad problem of performance；
3rd, can effectively solve the processing problem of nickeliferous solvay-type electroplating wastewater, the nickeliferous solvay-type electroplating wastewater of processing reaches plating Pollutant emission standard table 3 requires.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this. Involved number is mass fraction in following examples.
Embodiment one
First, ultrafast sedimentation type molecule brush configuration heavy metal chelating agent is prepared, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take 1 part azodiisobutyronitrile initiator, 200 parts of hydroxyethyl acrylamide（HEMAA）, 100 part methanol, in nitrogen Protect lower 80 DEG C to carry out polymerisation 4 hours, obtain the degree of polymerization（DP）For 230 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 functional polymer side chain precursor polymer PNVF-COOH
Take 1 part azo dicyano valeric acid initiator, 300 parts of N- vinyl formamides（NVF）With 300 parts of water, in nitrogen Protect lower 50 DEG C to carry out Raolical polymerizable 4 hours, obtain the degree of polymerization（DP）Gather for 50 functional polymer side chain presoma Compound PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
20 parts of CDTA and 20 parts of acetic anhydride are dissolved in 20 parts of 2- picolines, are controlled in 50 DEG C, react 20 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PVACDTANa-r-PVACS2Na)
1 part of main polymer chain PHEMAA and 20 parts of functional polymer resulting in step 2 obtained by taking in step 1 Side chain precursor polymer PNVF-COOH mixing is dissolved in 100 parts of water, add 1 part n-hydroxysuccinimide (NHS) and 1 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 10 hours at 50 DEG C, obtain Obtain Water-soluble Polymer Molecules brush PHEMAA-g-PNVF；；1 part of potassium hydroxide is added, temperature control is hydrolyzed anti-in 50 DEG C Answer 48 hours, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyvinylamine）（PHEMAA- PVA)；20 parts of CDTA dianhydride (CDTAD) obtained by adding in step 3, temperature control enter in 50 DEG C Row acylation reaction 24 hours, acylation degree 90%, obtain poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene diamine Tetraacethyl sodium-random-polyvinylamine）(PHEMAA-g-(PVACDTANa-r-PVA))；Add 1 part of carbon disulfide, temperature control In 20 DEG C, addition reaction 1 hour is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring oneself Sodium ethylene diamine tetracetate-random-polyethylene amido nabam）(PHEMAA-g-(PVACDTANa-r- PVACS2Na be)) ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, using nmr determination PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 18% and 2%.
In the present embodiment, the application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent
Ultrafast sedimentation type molecule brush configuration heavy metal chelating agent obtained by taking in the present embodiment does heavy metal wastewater thereby test, takes 100 parts contain 10 mg/L Ni2+Ion and 8 mg/L citric acid wastewaters, 0.1 part of ultrafast sedimentation type molecule brush configuration of addition In heavy metal chelating agent, stirred 1 minute under normal temperature, with 0.1 mol/L salt acid for adjusting pH to 3, add 0.02 part of calcium chloride, often The lower stirring of temperature generates the flco that particle diameter is more than 580 μm in 1 minute, 5 seconds and precipitated.After filtering, using atomic absorption spectrphotometry Meter measure Ni2+Ion concentration is 0.01 mg/L, removal efficiency>99%.
It is mass fraction above.
Embodiment two
First, ultrafast sedimentation type molecule brush configuration heavy metal chelating agent is prepared, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take 1 part azodiisobutyronitrile initiator, 400 parts of hydroxyethyl acrylamide（HEMAA）, 50 part methanol, in nitrogen Protect lower 70 DEG C to carry out polymerisation 9 hours, obtain the degree of polymerization（DP）For 570 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 functional polymer side chain precursor polymer PNVF-COOH
Take 1 part azo dicyano valeric acid initiator, 300 parts of N- vinyl formamides（NVF）With 100 parts of water, in nitrogen Protect lower 60 DEG C to carry out Raolical polymerizable 5 hours, obtain the degree of polymerization（DP）Gather for 120 functional polymer side chain presoma Compound PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
60 parts of CDTA and 60 parts of acetic anhydride are dissolved in 60 parts of 2- picolines, are controlled in 60 DEG C, react 30 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PVACDTANa-r-PVACS2Na)
1 part of main polymer chain PHEMAA and 60 parts of functional polymer resulting in step 2 obtained by taking in step 1 Side chain precursor polymer PNVF-COOH mixing is dissolved in 300 parts of water, adds 3 parts of n-hydroxysuccinimide (NHS) With 3 parts of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 50 hours at 60 DEG C, Obtain Water-soluble Polymer Molecules brush PHEMAA-g-PNVF；；5 parts of potassium hydroxide is added, temperature control is hydrolyzed in 60 DEG C Reaction 36 hours, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyvinylamine）（PHEMAA- PVA)；60 parts of CDTA dianhydride (CDTAD) obtained by adding in step 3, temperature control enter in 60 DEG C Row acylation reaction 12 hours, acylation degree 92%, obtain poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene diamine Tetraacethyl sodium-random-polyvinylamine）(PHEMAA-g-(PVACDTANa-r-PVA))；Add 5 parts of carbon disulfide, temperature control In 30 DEG C, addition reaction 2 hours is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring oneself Sodium ethylene diamine tetracetate-random-polyethylene amido nabam）(PHEMAA-g-(PVACDTANa-r- PVACS2Na be)) ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, using nmr determination PVACDTANa and PVACS2The grafting rate of Na side chains is respectively 54% and 4%.
In the present embodiment, the application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent
Then, the ultrafast sedimentation type molecule brush configuration heavy metal chelating agent obtained by the present embodiment is taken to do heavy metal wastewater thereby test, 500 parts are taken to contain 20 mg/L Ni2+Ion and 2 mg/L disodium ethylene diamine tetraacetate waste water, add 0.5 part of ultrafast sedimentation type point In sub- brush configuration heavy metal chelating agent, stirred 3 minutes under normal temperature, with 0.1 mol/L salt acid for adjusting pH to 6, add 0.02 part Magnesium sulfate, the flco precipitation for generating that particle diameter is more than 650 μm in 1 minute, 3 seconds is stirred under normal temperature.After filtering, using Atomic absorption Spectrophotometric determination Ni2+Ion concentration is 0.03 mg/L, removal efficiency>99%.
It is mass fraction above.
Embodiment three
First, ultrafast sedimentation type molecule brush configuration heavy metal chelating agent is prepared, is prepared by following steps：
Step 1 synthetic polymer main chain PHEMAA
Take 1 part azodiisobutyronitrile initiator, 500 parts of hydroxyethyl acrylamide（HEMAA）, 20 part methanol, in nitrogen Protect lower 60 DEG C to carry out polymerisation 10 hours, obtain the degree of polymerization（DP）For 850 poly-hydroxyethyl acrylamide（PHEMAA）；
Step 2 functional polymer side chain precursor polymer PNVF-COOH
Take 1 part azo dicyano valeric acid initiator, 300 parts of N- vinyl formamides（NVF）With 50 parts of water, protected in nitrogen Protect lower 70 DEG C and carry out Raolical polymerizable 6 hours, obtain the degree of polymerization（DP）It polymerize for 180 functional polymer side chain presoma Thing PNVF-COOH；
Step 3 synthesis 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD)
80 parts of CDTA and 80 parts of acetic anhydrides are dissolved in 80 parts of 2- picolines, are controlled in 70 DEG C, react 40 hours, obtain CDTA dianhydride；
Step 4 synthesis PHEMAA-g- (PVACDTANa-r-PVACS2Na)
2 parts of main polymer chain PHEMAA and 80 parts of functional polymer resulting in step 2 obtained by taking in step 1 Side chain precursor polymer PNVF-COOH mixing is dissolved in 500 parts of water, adds 5 parts of n-hydroxysuccinimide (NHS) With 5 parts of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), react 70 hours at 80 DEG C, Obtain Water-soluble Polymer Molecules brush PHEMAA-g-PNVF；9 parts of potassium hydroxide is added, temperature control is hydrolyzed anti-in 80 DEG C Answer 12 hours, obtain poly-hydroxyethyl acrylamide-grafting-（Polymethylacrylic acid receives-random-polyvinylamine）（PHEMAA- PVA)；80 parts of CDTA dianhydride (CDTAD) obtained by adding in step 3, temperature control enter in 80 DEG C Row acylation reaction 5 hours, acylation degree 94%, obtain poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyvinylamine）(PHEMAA-g-(PVACDTANa-r-PVA))；Add 3 parts of carbon disulfide, temperature control in 40 DEG C, addition reaction 3 hours is carried out, it is final to obtain water-soluble poly hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring oneself two Amine tetraacethyl sodium-random-polyethylene amido nabam）(PHEMAA-g-(PVACDTANa-r-PVACS2Na)) I.e. ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, using nmr determination PVACDTANa and PVACS2Na side chains Grafting rate be respectively 75% and 5%.
In the present embodiment, the application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent
Take the ultrafast sedimentation type molecule brush configuration heavy metal chelating agent obtained by the present embodiment to do heavy metal wastewater thereby test, take 1000 Part contains 10 mg/L Pb2+Ion, 8 mg/L Cu2+Ion, 6 mg/L Zn2+Ion, 5 mg/L Ni2+Ion and 2 mg/L Disodium ethylene diamine tetraacetate waste water, add in 1 part of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, 4 are stirred under normal temperature Minute, pH to 10 is adjusted with 1 mol/L potassium hydroxide, the wadding for generating that particle diameter is more than 780 μm in 1 minute, 2 seconds is stirred under normal temperature Body precipitates.After filtering, Pb is determined using atomic absorption spectrophotometer 2+Ion concentration is 0.0 1 mg/L, Cu2+Ion concentration For 0.04 mg/L, Zn 2+Ion concentration is 0.05 mg/L, Ni 2+Ion concentration is 0.01 mg/L, removal efficiency>99%.
It is mass fraction above.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (6)

1. a kind of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, it is characterised in that include 1~10 part of main polymer chain Poly-hydroxyethyl acrylamide（PHEMAA）, 1~80 part functional polymer side chain precursor polymer end it is carboxylic poly- N- vinyl formamides（PNVF-COOH）, 100~500 parts water, 1~5 part of catalyst be n-hydroxysuccinimide (NHS), 1~5 part of 1- ethyls -3- (3- dimethylamino-propyls) carbodiimide iodomethane salt (EDCCH3I), 1~10 part Potassium hydroxide, 1~80 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) and 1~10 part of carbon disulfide；It is matter above Measure number.
2. ultrafast sedimentation type molecule brush configuration heavy metal chelating agent according to claim 1, it is characterised in that the polymerization The poly-hydroxyethyl acrylamide of owner's chain（PHEMAA）It is to be synthesized by general radical polymerization or controllable living polymerization PHEMAA main polymer chains；The carboxylic polyvinylformamide in the functional polymer side chain precursor polymer end （PNVF-COOH）Azo dicyano valeric acid mainly is used as initiator, and it is carboxylic to polymerize synthesis end by general radical Polyvinylformamide（PNVF-COOH）Polymer；The synthesis side of the 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTAD) Method is that 1~80 part of 1,2- 1,2-diaminocyclohexane tetraacetic acids and 1~80 part of acetic anhydride are dissolved in 1~80 part of 2- picolines In, 50~70 DEG C are controlled in, is reacted 20~40 hours, obtains CDTA dianhydride；It is mass fraction above.
3. a kind of preparation method of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, it is characterised in that step is as follows：
Step 1 prepares poly-hydroxyethyl acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF)
By the poly-hydroxyethyl acrylamide of 1~10 part of main polymer chain（PHEMAA）With 1~80 part of functional polymer side chain The carboxylic polyvinylformamide in precursor polymer end（PNVF-COOH）Mixing is dissolved in 100~500 parts of water, The catalyst for adding 1~5 part is the 1- ethyls -3- (3- dimethylamino-propyls) of n-hydroxysuccinimide (NHS) and 1~5 part Carbodiimide iodomethane salt (EDCCH3I), temperature control carries out esterification 10~70 hours in 50~80 DEG C, obtains poly- hydroxyl second Base acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF)；
Step 2 prepares poly-hydroxyethyl acrylamide-grafting-polyvinylamine（PHEMAA-PVA)
Add in poly-hydroxyethyl acrylamide-grafting-polyvinylformamide (PHEMAA-g-PNVF) obtained by step 1 Entering 1~10 part of potassium hydroxide, in 50~80 DEG C reaction is hydrolyzed 12~48 hours in temperature control, acquisition poly-hydroxyethyl acrylamide- Grafting-polyvinylamine（PHEMAA-PVA)；
Step 3 prepares poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyethylene Amine）(PHEMAA-g-(PVACDTANa-r-PVA))
Poly-hydroxyethyl acrylamide-grafting-polyvinylamine obtained by step 2（PHEMAA-PVA 1~80 part is added in) CDTA dianhydride (CDTAD), carries out acylation reaction 5~24 hours, and acylation degree scope control is 80~ 99%, obtain poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyvinylamine） (PHEMAA-g-(PVACDTANa-r-PVA))；
Step 4 prepares the poly-hydroxyethyl acrylamide-grafting-of Water-soluble Polymer Molecules brush（Polyvinylamine basic ring hexamethylene diamine four Sodium acetate-random-polyethylene amido nabam）(PHEMAA-g-( PVACDTANa-r-PVACS2Na))
Poly-hydroxyethyl acrylamide-grafting-obtained by step 3（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-poly- Vinylamine）1~10 part of carbon disulfide is added in (PHEMAA-g- (PVACDTANa-r-PVA)), temperature control enters in 20~40 DEG C Row addition reaction 1~3 hour, it is final to obtain the poly-hydroxyethyl acrylamide-grafting-of Water-soluble Polymer Molecules brush（Polyvinylamine Basic ring hexamethylene tetraacetic acid sodium-random-polyethylene amido nabam）(PHEMAA-g-( PVACDTANa-r- PVACS2Na it is)) ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, is mass fraction above.
4. the preparation method of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent according to claim 3, its feature exist In the poly-hydroxyethyl acrylamide（PHEMAA）The degree of polymerization on 1~1000, functional polymer side chain presoma polymerization The thing PNVF-COOH degree of polymerization is 10~200, chelating type polymer side chain PVACDTANa grafting rate 5~80% and helps sedimentation Polymer side chain PVACS2Na grafting rate is 1~5%.
5. a kind of application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent, it is characterised in that by 0.1~1 part of water solubility Poly-hydroxyethyl acrylamide-grafting-（Polyvinylamine basic ring hexamethylene tetraacetic acid sodium-random-polyethylene amido dithiocarbamates first Sour sodium）(PHEMAA-g-(PVACDTANa-r-PVACS2Na)) be added in 100~1000 parts of waste water, under normal temperature stir 1~ 5 minutes, adjust pH to 1~14, heavy metal ions in wastewater and polymer molecule brush (PHEMAA-g- (PVACDTANa-r- PVACS2Chelating absorption occurs for chelating type side chain PVACDTANa Na)), adds 0.01~0.1 part of the sedimentation agent that helps, normal temperature It is lower stirring 1 minute, help sedimentation agent metal ion will quickly with Water-soluble Polymer Molecules brush (PHEMAA-g- (PVACDTANa- r-PVACS2Na sedimentation side chain PVACS is helped on))2Chemical precipitation reaction occurs for Na, and the wadding that particle diameter is more than 500 μm is generated in 5 seconds Body precipitates, and can quickly realize the solvay-type heavy metal ion removed in waste water, be mass fraction above.
6. the application of ultrafast sedimentation type molecule brush configuration heavy metal chelating agent according to claim 5, it is characterised in that institute State and help sedimentation agent as calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, one or more kinds of any groups of alchlor Close.
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