CN107879456A - Environmentally friendly dye of positive ion trapping agent and preparation method thereof and its application - Google Patents

Environmentally friendly dye of positive ion trapping agent and preparation method thereof and its application Download PDF

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Publication number
CN107879456A
CN107879456A CN201711127688.XA CN201711127688A CN107879456A CN 107879456 A CN107879456 A CN 107879456A CN 201711127688 A CN201711127688 A CN 201711127688A CN 107879456 A CN107879456 A CN 107879456A
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environmentally friendly
positive ion
parts
dye
trapping agent
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Inventor
刘锋
霍应鹏
陈燕舞
张浥琨
郭志杰
洪丹
彭琦
唐秋实
李为山
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Shunde Vocational and Technical College
Shunde Polytechnic
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Shunde Vocational and Technical College
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    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The present invention relates to a kind of environmentally friendly dye of positive ion trapping agent and preparation method thereof and its application, feature is to prepare environmentally friendly dye of positive ion trapping agent, and the waste water that environmentally friendly dye of positive ion trapping agent is used to handle the cationic dyes waste water given off in Dyestuff synthesis or dyeing and finishing process and the discharge of art coatings industry by konjaku glucomannan, methacrylic acid, N vinyl formamides, water, water soluble starter azo diisobutyl amidine hydrochloride V 50, sodium hydroxide and ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride.Its trapping ability is strong, sinking speed is fast, low concentration solvay-type heavy metal ion can be handled, trapping positive ions dye molecule and solvay-type heavy metal ion and fast-growth into big sedimented particle, the purpose of the quick separating dye of positive ion and heavy metal ion can be realized within the several seconds, it is nontoxic, environmentally friendly, it is degradable, secondary pollution is not easily caused in use, it is easy to operate, processing cost is low, strong adaptability.

Description

Environmentally friendly dye of positive ion trapping agent and preparation method thereof and its application
Technical field
The invention belongs to biological material and field of waste water treatment, and in particular to a kind of environmentally friendly dye of positive ion is caught Collect agent and preparation method thereof and its application, its cationic dyes waste water mainly given off in Dyestuff synthesis or dyeing and finishing process And applied in the waste water of art coatings industry discharge.
Background technology
In the last few years, the annual quantity of wastewater effluent in China is up to more than 390 hundred million tons, and wherein trade effluent accounts for 51%, and waste water from dyestuff The 35% of total discharged volume of industrial waste water is accounted for, but also is being increased year by year with 1% speed.Waste water from dyestuff by synthesize or dyeing and finishing process in The composition such as the dyestuff that gives off, auxiliary agent, mostlys come from Dyestuff synthesis and dyestuff uses enterprise, such as dyeing and coating row Industry.With the rapid development of printing and dyeing industry, China is textile production and processing big country, and row occupy textile exports volume for many years First place in the world, annual DYE PRODUCTION amount is up to 1.5 × 105Ton, wherein about 10%~15% dyestuff directly can be discharged into waste water In water body, waste water from dyestuff turns into one of important pollution sources of water body.Controlled to strengthen textile dyeing and finishing industrial water pollution, 2012, Environmental Protection Department and State Administration for Quality Supervision and Inspection and Quarantine's joint revision are issued《Textile dyeing and finishing industrial water pollution thing discharge mark It is accurate》(GB 4287-2012).According to new discharge standard, using traditional treatment technology, many printing and dyeing enterprises are unable to reach newly Discharging standards, occur it is many steal discharge phenomenons, there occurs serious water body environment pollution event.2015, with reference to spinning Garden actual conditions and the adjustment demand of the indirect emission control of water pollutant are knitted, are issued again《Textile dyeing and finishing industrial water pollution thing Discharge standard》(GB 4287-2012) amendment (Environmental Protection Department announce 2015 No. 19), reduces discharge standard, repaiies Change as follows：First, the phenyl amines of table 2 and table 3, Cr VI emission control requirement in temporary respite GB 4287-2012, in the postponement phase Phenyl amines, Cr VI perform the related request of table 1.2nd, " waste water enters town sewage in the GB 4287-2012 amendment that falls into abeyance Treatment plant discharges via town sewage pipeline, should reach direct emission limit ".On the whole, current dye wastewater treatment Technology is also unable to reach discharging standards, and the research and development for being badly in need of new material and new technology solve current enterprise's emission problem.Dyestuff Waste water has extremely strong pollution sense, and colored water knows from experience influence solar radiation, is unfavorable for the growth of aquatile, and in general is biochemical Method is difficult that it is handled.The discharge capacity of waste water from dyestuff is also very big, and discharges with intermittence, and water quality is also unstable, category In refractory reason waste water.
Traditional method of wastewater treatment has physico-chemical process, chemical coagulation process, physisorphtion, biochemical process, electrochemical process etc..Change It is that coagulant is added in waste water from dyestuff to learn Coagulation Method, pollutant is formed micelle, by coagulating sedimentation or air supporting, so as to remove Pollutant in waste water.Coagulant sedimentation is widest in practical application.Coagulation Method can remove dyestuff contaminant and its simultaneously His macromolecular suspended contaminant.The structural property of coagulant is depended primarily on to the treatment effect of waste water.What is used at present is mixed Solidifying agent mainly has inorganic coagulant and organic polymer coagulant.Inorganic coagulant is mainly based on aluminium salt and molysite, to glue The dyestuff that body or suspended state are present in waste water has preferable coagulation effect, but smaller for water-soluble dye middle-molecular-weihydroxyethyl , coagulation effect is then poor.Organic polymer coagulant molecular weight is big, and huge number of linear point is separated into after dissolving in water Son is strong to the adsorption bridging ability of the colloidal suspension particle in water.Organic polymer coagulant property is stable, and growth is fast, residue It is few, wider is required to pH value, is exactly polyacrylamide wherein most representative, but polyacrylamide non-degradable, easily draw Send out secondary pollution.In recent years, the coagulant for novel degradable being developed with chitosan biological material obtained development, can partly substitute Synthesize high polymer polyacrylamide.The degradable coagulant processing waste water from dyestuff major defect of chitosan class is that sinking speed is slow, Waste water from dyestuff can not quickly be handled.High molecular Coagulation Method is easy to operate, and processing cost is low, strong adaptability, high treating effect, and The exploitation of various novel coagulants always is the study hotspot of association area.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art and provides a kind of environmentally friendly dye of positive ion trapping agent And preparation method thereof and its application, trapping ability is strong, and sinking speed is fast, can handle low concentration solvay-type heavy metal ion, can be Trapping positive ions dye molecule and solvay-type heavy metal ion and fast-growth realize quick point into big sedimented particle in several seconds The purpose of cations dyestuff and heavy metal ion, it is nontoxic, environmentally friendly, it is degradable, secondary pollution is not easily caused in use, Easy to operate, processing cost is low, strong adaptability.
To achieve these goals, the technical scheme of environmentally friendly dye of positive ion trapping agent of the invention is such reality Existing, it is characterised in that the konjaku glucomannan including 1~5 part, 5~20 parts of methacrylic acid（MAA）, 1~15 part of N- Vinyl formamide（NVF）, 50~200 parts water, 0.1~1 part of water soluble starter azo diisobutyl amidine hydrochloride V- 50th, 1~10 part of sodium hydroxide and 1~30 part of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD）；They are mass parts Number.
To achieve these goals, the technical side of the preparation method of environmentally friendly dye of positive ion trapping agent of the invention Case, which is achieved in that, is characterized in that preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 1~5 part of konjaku glucomannan（KGM）Be added to 50~200 parts of water, 40~70 DEG C of temperature control, carry out dissolving 0.5~ 1 hour；Under nitrogen protection, the initiator azo diisobutyl amidine hydrochloride V-50 of 0.1~1 part of addition, 5~20 parts of methyl Acrylic acid（MAA）With 1~15 part of N- vinyl formamides（NVF）, graft copolymerization 1~20 hour, cooling stopping reaction；Add 50~200 parts of ethanol carries out precipitation separation, filtering and after drying, and obtains high-purity konjaku glucomannan-grafting-poly-（Methyl Acrylic acid-random-N- vinyl formamides）Copolymer (KGM-g-P (MAA-r-NVF)), wherein g represent grafting, and r represents random Copolymerization；They are mass fraction；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
20~40 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 20~40 parts of acetic anhydride are dissolved in 30~60 parts of 2- In picoline, 50~70 DEG C are controlled in, is reacted 20~40 hours, obtains ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；They For mass fraction；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
Take 1~5 part of KGM-g-P (MAA-r-NVF), add 50~200 parts of water, 50~80 DEG C of temperature control, under mechanical stirring Dissolving 1~2 hour；Add 1~10 part of sodium hydroxide, hydrolysis 12~48 hours, acquisition konjaku glucomannan-connect Branch-poly-（Sodium methacrylate-random-vinylamine）Copolymer KGM-g-P (MAANa-r-VA)；Add 1~30 part of second two Diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD）, vinylamine is acylated anti-with the generation of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride Answer 12~48 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random-vinylamine ethyl glycol diethyl ether Sodium ethylene diamine tetracetate）（KGM-g-P(MAANa-r-VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent；They are matter Measure number.
In the technical program, the Sodium methacrylate（MAANa）Grafting rate be 5~100%, ethene amido second two Diethylene glycol diethyl ether sodium ethylene diamine tetracetate（VAEGTANa）Grafting rate be 1~50%.
To achieve these goals, the technical scheme of the application of environmentally friendly dye of positive ion trapping agent of the invention is It is achieved in that, it is characterised in that take 100~1000 parts of waste water, add 0.1~1 part of the environmentally friendly dye of positive ion and catch Collect agent, stirred 1~5 minute under normal temperature, adjust pH to 6~9, waste water cationic dyestuff is caught with the environmentally friendly dye of positive ion Electrostatic Absorption, heavy metal ions in wastewater and environmentally friendly dye of positive ion trapping agent occur for the MAANa functional groups for collecting agent VAEGTANa functional groups occur chelant absorption, the dye of positive ion and heavy metal ion will be adsorbed in konjaku glucomannan completely On copolymer macromolecular scaffold；0.01~0.1 part of the sedimentation agent that helps is added, is stirred 1 minute under normal temperature, helps the excess of sedimentation agent Quickly with the VAEGTANa on konjak portuguese gansu polyose sugar copolymer chelation crosslinking precipitation reaction will occur for metal ion, be generated in 10 seconds Flco of the particle diameter more than 100 μm precipitates, and quickly realizes the dye of positive ion and heavy metal ion separation of solid and liquid, and water outlet is substantially colorless, Reach discharging standards；They are mass fraction.
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 is had the following advantages relative to prior art and effect：
1st, solve the problems, such as that conventional polymer flocculant sinking speed is slow, the present invention has dual-use function, can trapping positive ions Dyestuff and solvay-type heavy metal ion, can be by electrostatic interaction rapid acquiring cationic dyes, will a huge sum of money by chelation Belong to ion chelating in the chelate functional that on konjaku glucomannan molecular skeleton, and can is grafted by konjaku glucomannan molecular skeleton Group generates big aggregation, so as to realize with helping precipitating reagent excess metal ion that chelant precipitation reaction quickly occurs within the several seconds Rapid subsidence；
2nd, the present invention is a kind of environmentally friendly material, nontoxic, environmentally friendly, degradable, does not easily cause secondary dirt in use Dye.
3rd, preparation technology of the present invention is simple, and caused sludge quantity is few, easy to operate, and processing cost is low, strong adaptability.
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
It is a kind of environmentally friendly dye of positive ion trapping agent, and preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 2 parts and konjaku glucomannan（KGM）, 50 parts and water are added, 45 DEG C of temperature control, carries out dissolving 0.5 hour；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,6 parts of the methacrylic acid of 0.1 part of addition（MAA）With 3 parts of N- second Alkenyl formamide（NVF）, polymerisation 3 hours, cooling stopping reaction；Add 50 parts of ethanol and carry out precipitation separation, filtering and After drying, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid-random-N- vinyl formamides）Copolymer (KGM-g-P(MAA-r-NVF)).Use elementary analysis and nuclear magnetic resonance apparatus analyze the grafting rate of measure methacrylic acid for 24%, N- vinyl formamide grafting rate are 4%；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
20 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 20 parts of acetic anhydrides are dissolved in 30 parts of 2- picolines, are controlled in 50 DEG C, react 20 hours, obtain ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
2 parts of KGM-g-P (MAA-r-NVF) is taken, 50 parts of water is added, 50 DEG C of temperature control, dissolves 1 hour under mechanical stirring；Add Enter 2 parts of sodium hydroxide, hydrolysis 12 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random-second Enamine）Copolymer KGM-g-P (MAANa-r-VA)；10 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD) is added, Vinylamine and excessive ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 12 hours, obtain konjaku glucomannan-connect Branch-poly-（Sodium methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium）（KGM-g-P(MAANa-r- VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent；Using elementary analysis and nuclear magnetic resonance apparatus analysis measure ethene Amido ethylene glycol diethyl ether sodium ethylene diamine tetracetate grafting rate is 4%.
In the present embodiment, environmentally friendly dye of positive ion trapping agent is applied to Treatment of Cationic Dyestuff Wastewater
100 parts of the 40 mg/L methylene blue dye wastewaters that contain are taken, add 0.1 part of environmentally friendly dye of positive ion trapping agent, Stirred 1 minute under normal temperature, with 0.1mol/L salt acid for adjusting pH to 6, add 0.01 part of magnesium sulfate, stirred 1 minute under normal temperature, The flco that particle diameter is more than 150 μm is generated in 10 seconds to precipitate.After filtering, methylene blue concentration is determined using ultraviolet specrophotometer For 0.056 mg/L, removal efficiency>99%.
Embodiment two
It is a kind of environmentally friendly dye of positive ion trapping agent, and preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 3 parts of konjaku glucomannan（KGM）150 parts of water is added, 55 DEG C of temperature control, carries out dissolving 0.7 hour；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,13 parts of the methacrylic acid of 0.5 part of addition（MAA）With 7 parts of N- second Alkenyl formamide（NVF）, graft copolymerization 8 hours, cooling stopping reaction；Add 150 parts of ethanol and carry out precipitation separation, filtering and After drying, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid-random-N- vinyl formamides）Copolymer (KGM-g-P(MAA-r-NVF)).Use elementary analysis and nuclear magnetic resonance apparatus analyze the grafting rate of measure methacrylic acid for 40%, N- vinyl formamide grafting rate are 9%；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
30 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 30 parts of acetic anhydride are dissolved in 40 parts of 2- picolines, controlled In 60 DEG C, react 30 hours, obtain ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
3 parts of KGM-g-P (MAA-r-NVF) is taken, adds 150 parts of 60 DEG C of water control temperature, is dissolved 1.5 hours under mechanical stirring； Add 5 parts of sodium hydroxide, hydrolysis 24 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random- Vinylamine）Copolymer KGM-g-P (MAANa-r-VA)；20 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydrides (EGTAD) are added, Vinylamine and excessive ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 24 hours, obtain konjaku glucomannan-connect Branch-poly-（Sodium methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium）（KGM-g-P(MAANa-r- VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent；Using elementary analysis and nuclear magnetic resonance measuring ethene amido second two Diethylene glycol diethyl ether sodium ethylene diamine tetracetate grafting rate is 9%.
In the present embodiment, environmentally friendly dye of positive ion trapping agent is applied to Treatment of Cationic Dyestuff Wastewater
Take 300 parts containing 30 mg/L crystal violets, 3 mg/L Pb2+Ion and 0.2 mg/L citric acid waste water from dyestuff, add 0.3 Part environmentally friendly dye of positive ion trapping agent, stir 2 minutes under normal temperature, with 0.1mol/L sodium hydroxides regulation pH to 8, then 0.04 part of calcium chloride is added, the flco precipitation for generating that particle diameter is more than 150 μm in 1 minute, 6 seconds, filtering are stirred under normal temperature Afterwards, ultraviolet specrophotometer and atomic absorption spectrophotometer is used to determine crystal violet concentration as 0.056 mg/L and Pb2+Ion Concentration is 0.02 mg/L, removal efficiency>99%.
Embodiment three
It is a kind of environmentally friendly dye of positive ion trapping agent, and preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 4 parts of konjaku glucomannan（KGM）180 parts of water is added, 65 DEG C of temperature control, carries out dissolving 0.7 hour；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,16 parts of the methacrylic acid of 0.6 part of addition（MAA）With 13 parts of N- Vinyl formamide（NVF）, graft copolymerization 16 hours, cooling stopping reaction；Add 180 parts of ethanol and carry out precipitation separation, mistake Filter and after drying, obtain high-purity konjaku glucomannan-grafting-poly-（Methacrylic acid-random-N- vinyl formamides）Copolymerization Thing (KGM-g-P (MAA-r-NVF))；Use elementary analysis and nuclear magnetic resonance apparatus analyze the grafting rate of measure methacrylic acid for 67%, N- vinyl formamide grafting rate are 16%；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
35 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 35 parts of acetic anhydrides are dissolved in 50 parts of 2- picolines, are controlled in 65 DEG C, react 35 hours, obtain ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
4 parts of KGM-g-P (MAA-r-NVF) is taken, adds 180 parts of 60 DEG C of water control temperature, is dissolved 1.8 hours under mechanical stirring； Add 7 parts of sodium hydroxide, hydrolysis 36 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random- Vinylamine）Copolymer KGM-g-P (MAANa-r-VA)；Add 25 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD), vinylamine and excessive ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 36 hours, obtains Amorphophallus rivieri glucomannan Glycan-grafting-poly-（Sodium methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium）（KGM-g-P (MAANa-r-VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent；Using elementary analysis and nuclear magnetic resonance measuring second Enamine ethyl glycol ethyl ether diaminetetraacetic acid sodium grafting rate is 16%.
In the present embodiment, environmentally friendly dye of positive ion trapping agent is applied to Treatment of Cationic Dyestuff Wastewater
Take 500 parts containing 40 mg/L malachite greens, 3 mg/L Cd2+Ion and 0.2 mg/L citric acid waste water from dyestuff, add 0.5 part of environmentally friendly dye of positive ion trapping agent, stir 3 minutes under normal temperature, with 0.1mol/L sodium hydroxides adjust pH to 8,0.06 part of iron chloride is added, the flco precipitation for generating that particle diameter is more than 360 μm in 1 minute, 4 seconds is stirred under normal temperature.Cross After filter, ultraviolet specrophotometer and atomic absorption spectrophotometer measure malachite green concentration are 0.078 mg/L and Cd 2+Ion Concentration is 0.03mg/L, removal efficiency>99%.
Example IV
It is a kind of environmentally friendly dye of positive ion trapping agent, and preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 5 parts of konjaku glucomannan（KGM）200 parts of water is added, 70 DEG C of temperature control, carries out dissolving 1 hour；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,20 parts of the methacrylic acid of 1 part of addition（MAA）With 15 parts of N- second Alkenyl formamide（NVF）, it polymerize 19 hours, cooling stops reaction；Add 200 parts of ethanol and carry out precipitation separation, filter and dry After dry, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid-random-N- vinyl formamides）Copolymer (KGM-g-P(MAA-r-NVF)).Use elementary analysis and nuclear magnetic resonance apparatus analyze the grafting rate of measure methacrylic acid for 97%, N- vinyl formamide grafting rate are 35%；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
40 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 40 parts of acetic anhydride are dissolved in 60 parts of 2- picolines, controlled In 70 DEG C, react 40 hours, obtain ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
5 parts of KGM-g-P (MAA-r-NVF) is taken, adds 180 parts of 60 DEG C of water control temperature, is dissolved 2 hours under mechanical stirring；Add Enter 10 parts of sodium hydroxide, hydrolysis 48 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random-second Enamine）Copolymer KGM-g-P (MAANa-r-VA)；30 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD) is added, Vinylamine and excessive ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 48 hours, obtain konjaku glucomannan-connect Branch-poly-（Sodium methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium）（KGM-g-P(MAANa-r- VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent, using elementary analysis and nuclear magnetic resonance measuring ethene amido second two Diethylene glycol diethyl ether sodium ethylene diamine tetracetate grafting rate is 35%.
In the present embodiment, environmentally friendly dye of positive ion trapping agent is applied to Treatment of Cationic Dyestuff Wastewater
Take 1000 parts containing 40 mg/L crystal violets, 5 mg/L Ni2+Ion and 0.5 mg/L citric acid waste water from dyestuff, add 1 part Environmentally friendly dye of positive ion trapping agent, stir 5 minutes under normal temperature, adjust pH to 9 with 0.1mol/L sodium hydroxides, then add Enter 0.1 part of aluminium chloride, the flco precipitation for generating that particle diameter is more than 450 μm in 1 minute, 2 seconds is stirred under normal temperature, it is purple after filtering Outer spectrophotometer and atomic absorption spectrophotometer measure crystal violet concentration is 0.087 mg/L and Ni2+Ion concentration is 0.03mg/L, removal efficiency>99%.
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 (5)

1. a kind of environmentally friendly dye of positive ion trapping agent, it is characterised in that the konjaku glucomannan including 1~5 part, 5~20 The methacrylic acid of part（MAA）, 1~15 part of N- vinyl formamides（NVF）, 50~200 parts water, 0.1~1 part water-soluble Property initiator azo diisobutyl amidine hydrochloride V-50,1~10 part of sodium hydroxide and 1~30 part of ethylene glycol diethyl ether diamines Tetrem acid dianhydride (EGTAD）；They are mass fraction.
2. a kind of preparation method of environmentally friendly dye of positive ion trapping agent, it is characterised in that preparation process is as follows：
Step 1 KGM-g-P (MAA-r-NVF) synthesis
By 1~5 part of konjaku glucomannan（KGM）Be added to 50~200 parts of water, 40~70 DEG C of temperature control, carry out dissolving 0.5~ 1 hour；Under nitrogen protection, the initiator azo diisobutyl amidine hydrochloride V-50 of 0.1~1 part of addition, 5~20 parts of methyl Acrylic acid（MAA）With 1~15 part of N- vinyl formamides（NVF）, graft copolymerization 1~20 hour, cooling stopping reaction；Add 50~200 parts of ethanol carries out precipitation separation, filtering and after drying, and obtains high-purity konjaku glucomannan-grafting-poly-（Methyl Acrylic acid-random-N- vinyl formamides）Copolymer (KGM-g-P (MAA-r-NVF)), wherein g represent grafting, and r represents random Copolymerization；They are mass fraction；
The synthesis of step diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)
20~40 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) and 20~40 parts of acetic anhydride are dissolved in 30~60 parts of 2- first In yl pyridines, 50~70 DEG C are controlled in, is reacted 20~40 hours, obtains ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；They are Mass fraction；
Step 3 KGM-g-P (MAANa-r-VAEGTANa) synthesis
Take 1~5 part of KGM-g-P (MAA-r-NVF), add 50~200 parts of water, 50~80 DEG C of temperature control, under mechanical stirring Dissolving 1~2 hour；Add 1~10 part of sodium hydroxide, hydrolysis 12~48 hours, acquisition konjaku glucomannan-connect Branch-poly-（Sodium methacrylate-random-vinylamine）Copolymer KGM-g-P (MAANa-r-VA)；Add 1~30 part of second two Diethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD）, vinylamine is acylated anti-with the generation of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride Answer 12~48 hours, acquisition konjaku glucomannan-grafting-poly-（Sodium methacrylate-random-vinylamine ethyl glycol diethyl ether Sodium ethylene diamine tetracetate）（KGM-g-P(MAANa-r-VAEGTANa)）I.e. environmentally friendly dye of positive ion trapping agent；They are matter Measure number.
3. the preparation method of environmentally friendly dye of positive ion trapping agent according to claim 2, it is characterised in that described Sodium methacrylate（MAANa）Grafting rate be 5~100%, vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium （VAEGTANa）Grafting rate be 1~50%.
4. a kind of application of environmentally friendly dye of positive ion trapping agent, it is characterised in that take 100~1000 parts of waste water, add 0.1~1 part of environmentally friendly dye of positive ion trapping agent, stir 1~5 minute under normal temperature, adjust pH to 6~9, waste water middle-jiao yang, function of the spleen and stomach Electrostatic Absorption, heavy metal in waste water occur for the MAANa functional groups of ionic dye and environmentally friendly dye of positive ion trapping agent Chelant absorption occurs for the VAEGTANa functional groups of ion and environmentally friendly dye of positive ion trapping agent, the dye of positive ion and again Metal ion will be adsorbed on konjak portuguese gansu polyose sugar copolymer macromolecular scaffold completely；Add 0.01~0.1 part and help sedimentation Agent, stir 1 minute under normal temperature, help the excess metal ion of sedimentation agent by quickly with konjak portuguese gansu polyose sugar copolymer Chelation crosslinking precipitation reaction occurs for VAEGTANa, and flco of the particle diameter more than 100 μm is generated in 10 seconds and is precipitated, it is quick realize sun from Sub- dyestuff and heavy metal ion separation of solid and liquid, water outlet is substantially colorless, reaches discharging standards；They are mass fraction.
5. the application of environmentally friendly dye of positive ion trapping agent according to claim 4, it is characterised in that described to help sedimentation Agent is calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, one or more kinds of any combination of alchlor.
CN201711127688.XA 2017-11-15 2017-11-15 Environmentally friendly dye of positive ion trapping agent and preparation method thereof and its application Withdrawn CN107879456A (en)

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CN1401678A (en) * 2002-09-12 2003-03-12 武汉大学 Konjaku plucosidopolyose graft copolymer, preparing process and use thereof
CN101884909A (en) * 2010-06-29 2010-11-17 湖北工业大学 Method for preparing konjac glucomannan adsorbing material
CN105498726A (en) * 2015-12-17 2016-04-20 山东大学 High-adsorptivity heavy metal ion chelating agent containing dithiocar-bamate structure and preparation method thereof

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CN1401678A (en) * 2002-09-12 2003-03-12 武汉大学 Konjaku plucosidopolyose graft copolymer, preparing process and use thereof
CN101884909A (en) * 2010-06-29 2010-11-17 湖北工业大学 Method for preparing konjac glucomannan adsorbing material
CN105498726A (en) * 2015-12-17 2016-04-20 山东大学 High-adsorptivity heavy metal ion chelating agent containing dithiocar-bamate structure and preparation method thereof

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Application publication date: 20180406