CN107915804A - Environmentally friendly anionic dye trapping agent and preparation method thereof and its application - Google Patents

Environmentally friendly anionic dye trapping agent and preparation method thereof and its application Download PDF

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Publication number
CN107915804A
CN107915804A CN201711127657.4A CN201711127657A CN107915804A CN 107915804 A CN107915804 A CN 107915804A CN 201711127657 A CN201711127657 A CN 201711127657A CN 107915804 A CN107915804 A CN 107915804A
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environmentally friendly
parts
anionic dye
daema
trapping agent
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of environmentally friendly anionic dye trapping agent and preparation method thereof and its application, feature is by konjaku glucomannan, diethylaminoethyl methacrylate, N vinyl formamides, water, water soluble starter azo diisobutyl amidine hydrochloride V 50, potassium hydroxide and ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride prepare environmentally friendly anionic dye trapping agent, and environmentally friendly anionic dye trapping agent trapping ability to be used for by force to the waste water for handling the anionic dyes waste water given off in Dyestuff synthesis or dyeing and finishing process and the discharge of art coatings industry.It is fast with sinking speed, low concentration solvay-type heavy metal ion can be handled, can trapping negative ions dye molecule and solvay-type heavy metal ion in a few seconds, for fast-growth into big sedimented particle, realization separates the purpose of anionic dye and heavy metal ion, nontoxic, environmentally friendly, it is degradable, the advantages that secondary pollution is easy to operate, and processing cost is low, adaptable is not easily caused in use.

Description

Environmentally friendly anionic dye 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 anionic dye is caught Collect agent and preparation method thereof and its application, its anionic 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 recent years, the annual quantity of wastewater effluent in China is up to more than 390 hundred million tons, 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 can be directly discharged into waste water In water body, waste water from dyestuff becomes 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, and are issued《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 1 related request of table.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, general biochemistry 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, belongs to In refractory reason waste water.
Traditional wastewater treatment method 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 at the same time His macromolecular suspended contaminant.The structural property of coagulant is depended primarily upon 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 stablized, and growth is fast, residue It is few, pH value is required wider, be exactly polyacrylamide wherein most representative, but polyacrylamide non-degradable, easily draw Send out secondary pollution.In recent years, development was obtained with the coagulant of chitosan biological material exploitation novel degradable, can partly substituted 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, adaptable, high treating effect, and The exploitation of various novel coagulants always is the research hotspot of association area.
The content of the invention
A kind of environmentally friendly anionic dye trapping agent is provided the purpose of the present invention is overcome the deficiencies in the prior art 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 negative ions dye molecule and solvay-type heavy metal ion in several seconds, fast-growth realize that separation is cloudy into big sedimented particle The purpose of ionic dye and heavy metal ion, it is nontoxic, environmentally friendly, it is degradable, do not easily cause secondary pollution operation in use Simplicity, processing cost is low, adaptable.
To achieve these goals, the technical solution of environmentally friendly anionic dye 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 diethylaminoethyl methacrylate (DAEMA), 1~15 part of N- vinyl formamides (NVF), 50~200 parts of water, 0.1~1 part of water soluble starter azo Diisobutyl amidine hydrochloride V-50,1~10 part of potassium hydroxide and 1~30 part of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)；They are mass fraction.
To achieve these goals, the technical side of the preparation method of environmentally friendly anionic dye trapping agent of the invention Case, which is achieved in that, is characterized in that preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
1~5 part of konjaku glucomannan (KGM) is added to 50~200 parts of water, 40~70 DEG C of temperature control, carries 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 Diethylaminoethyl acrylate (DAEMA) and 1~15 part of N- vinyl formamides (NVF), when graft copolymerization 1~20 is small, drop Temperature stops reaction；Add 50~200 parts of ethanol and carry out precipitation separation, after filtering and drying, obtain high-purity konjak portuguese gansu polyose Sugar-grafting-poly- (diethylaminoethyl methacrylate-random-N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r- NVF)), wherein g represents 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, when reaction 20~40 is small are controlled in, obtains ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；They are Mass fraction；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
1~5 part of KGM-g-P (DAEMA-r-NVF) is taken, adds 50~200 parts of water, 50~80 DEG C of temperature control, in mechanical agitation It is lower dissolving 1~2 it is small when；1~10 part of potassium hydroxide is added, when hydrolysis 12~48 is small, acquisition konjaku glucomannan-connect Branch-poly- (diethylaminoethyl methacrylate-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 1~ 30 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD), vinylamine and ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acyl When glycosylation reaction 12~48 is small, konjaku glucomannan-grafting-poly- (diethylaminoethyl methacrylate-random-ethene is obtained Amido ethylene glycol diethyl ether sodium ethylene diamine tetracetate) (KGM-g-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anion Dyestuff trapping agent；They are mass fraction.
In the technical program, the grafting rate of the diethylaminoethyl methacrylate (DAEMA) is 5~100%, second The grafting rate of enamine ethyl glycol ethyl ether diaminetetraacetic acid sodium (VAEGTANa) is 1~50%.
To achieve these goals, the technical solution of the application of environmentally friendly anionic dye 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 environmentally friendly anionic dye and catch Collect agent, stirred 1~5 minute under room temperature, adjust pH to 2~5, anionic dye is caught with environmentally friendly anionic dye in waste water Electrostatic Absorption, heavy metal ions in wastewater and environmentally friendly anionic dye trapping agent occur for the DAEMA functional groups for collecting agent VAEGTANa functional groups occur chelant absorption, anionic dye 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 room temperature, helps the excess of sedimentation agent Metal ion will quickly with konjak portuguese gansu polyose sugar copolymer VAEGTANa functional groups occur chelation crosslinking precipitation reaction, 10 Flco of the generation particle diameter more than 100 μm precipitates in second, quickly realizes anionic dye and heavy metal ion separation of solid and liquid, goes out water base This is colourless, reaches discharging standards.
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 the 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 negative ions Dyestuff and solvay-type heavy metal ion, can be by electrostatic interaction rapid acquiring anionic dyes, will a huge sum of money by chelation Belong to ion chelating on konjaku glucomannan molecular skeleton, further handed over helping precipitating reagent excess metal ion that chelant quickly occurs Join precipitation reaction, big aggregation is generated in a few seconds, so as to fulfill 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 process of the present invention is simple, and the sludge quantity of generation is few, easy to operate, and processing cost is low, adaptable.
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 embodiments.
Embodiment one
It is a kind of environmentally friendly anionic dye trapping agent, and preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
By 2 parts of konjaku glucomannans (KGM) add 50 parts of water, 48 DEG C of temperature control, carry out dissolving 0.5 it is small when；Under nitrogen protection, Add 0.1 part of initiator azo diisobutyl amidine hydrochloride V-50,5 parts of diethylaminoethyl methacrylate (DAEMA) With 4 parts of N- vinyl formamides (NVF), when graft copolymerization 4 is small, cooling stops reaction；50 parts of ethanol is added to be precipitated Separation, filtering and it is dry after, obtain high-purity konjaku glucomannan-grafting-poly- (diethylaminoethyl methacrylate-random- N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r-NVF))；Surveyed using elemental analysis and nuclear magnetic resonance apparatus analysis The grafting rate for determining diethylaminoethyl methacrylate is that the grafting rate of 23%, N- vinyl formamides is 5%；
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 anhydride are dissolved in 30 parts of 2- picolines, controlled In 50 DEG C, when reaction 20 is small, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride is obtained；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
2 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 50 parts of 50 DEG C of water control temperature, when dissolving 1 is small under mechanical stirring；Add Enter 2 parts of potassium hydroxide, when hydrolysis 12 is small, obtain konjaku glucomannan-grafting-poly- (methacrylic acid lignocaine second Ester-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 10 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) two When acid anhydride (EGTAD), vinylamine and small ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 12, konjak portuguese gansu polyose is obtained Sugar-grafting-poly- (diethylaminoethyl methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium) (KGM- G-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anionic dye trapping agent；Surveyed using elemental analysis and nuclear magnetic resonance The grafting rate for determining vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium is 5%.
In the present embodiment, environmentally friendly anionic dye trapping agent is applied to anionic dye waste water processing
100 parts 40 mg/L reactive brilliant reds (K-2BP) waste water from dyestuff that contain are taken, add 0.1 part of environmentally friendly anionic dye Trapping agent, is stirred 1 minute under room temperature, with 0.1 mol/L salt acid for adjusting pH to 2, is added 0.01 part of magnesium sulfate, is stirred under room temperature Mix the flco precipitation for generating that particle diameter is more than 160 μm in 1 minute, 10 seconds.After filtering, activity is measured using ultraviolet specrophotometer Bright red concentration is 0.045mg/L, removal efficiency>99%.
Embodiment two
It is a kind of environmentally friendly anionic dye trapping agent, and preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
3 parts of konjaku glucomannans (KGM) are added into 150 parts of water, 55 DEG C of temperature control, carry out dissolving 0.7 it is small when；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,14 parts of the diethylaminoethyl methacrylate of 0.6 part of addition (DAEMA) and 9 parts of N- vinyl formamides (NVF), when graft copolymerization 7 is small, cooling stops reaction；Add 150 parts of ethanol Precipitation separation is carried out, after filtering and drying, obtains high-purity konjaku glucomannan-grafting-poly- (methacrylic acid lignocaine second Ester-random-N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r-NVF))；Using elemental analysis and Nuclear Magnetic Resonance The grafting rate of device analysis measure diethylaminoethyl methacrylate is that 46%, N- vinyl formamides grafting rate is 11%；
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, when reaction 30 is small, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride is obtained；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
3 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 150 parts of 60 DEG C of water control temperature, it is small to dissolve 1.5 under mechanical stirring When；5 parts of potassium hydroxide is added, when hydrolysis 24 is small, obtains konjaku glucomannan-grafting-poly- (methacrylic acid diethylamino Base ethyl ester-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 20 parts of ethylene glycol diethyl ether diamines tetrem When acid dianhydride (EGTAD), vinylamine and small ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 24, Amorphophallus rivieri glucomannan is obtained Glycan-grafting-poly- (diethylaminoethyl methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium) (KGM-g-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anionic dye trapping agent, using elemental analysis and nuclear-magnetism The grafting rate of resonance measure vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium is 11%.
In the present embodiment, environmentally friendly anionic dye trapping agent is applied to anionic dye waste water processing
Take 300 parts containing 30 mg/L Acid Light Yellow Gs, 4 mg/L Cd2+Ion and 0.2 mg/L citric acid waste water from dyestuff, add 0.3 part of environmentally friendly anionic dye trapping agent, is stirred 1 minute under room temperature, with 0.1 mol/L hydrochloric acid adjust pH to 3,0.04 part of aluminium chloride is added, the flco precipitation for generating that particle diameter is more than 280 μm in 1 minute, 8 seconds, mistake are stirred under room temperature After filter, ultraviolet specrophotometer and atomic absorption spectrophotometer is used to measure Acid Light Yellow G concentration as 0.085 mg/L and Cd2+ Ion concentration is 0.03 mg/L, removal efficiency>99%.
Embodiment three
It is a kind of environmentally friendly anionic dye trapping agent, and preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
4 parts of konjaku glucomannans (KGM) are added into 180 parts of water, 65 DEG C of temperature control, carry out dissolving 0.7 it is small when；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,17 parts of the diethylaminoethyl methacrylate of 0.7 part of addition (DAEMA) and 13 parts of N- vinyl formamides (NVF), when graft copolymerization 15 is small, cooling stops reaction；Add 180 parts of second Alcohol carries out precipitation separation, after filtering and drying, obtains high-purity konjaku glucomannan-grafting-poly- (methacrylic acid lignocaine Ethyl ester-random-N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r-NVF))；Using elemental analysis and nuclear magnetic resonance The grafting rate of Instrumental Analysis measure diethylaminoethyl methacrylate is that 78%, N- vinyl formamides grafting rate is 19%；
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 anhydride are dissolved in 55 parts of 2- picolines, controlled In 65 DEG C, when reaction 35 is small, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride is obtained；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
4 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 180 parts of 65 DEG C of water control temperature, it is small to dissolve 1.8 under mechanical stirring When；7 parts of potassium hydroxide is added, when hydrolysis 36 is small, obtains konjaku glucomannan-grafting-poly- (methacrylic acid diethylamino Base ethyl ester-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 30 parts of ethylene glycol diethyl ether diamines tetrem When acid dianhydride (EGTAD), vinylamine and small ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 36, Amorphophallus rivieri glucomannan is obtained Glycan-grafting-poly- (diethylaminoethyl methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium) (KGM-g-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anionic dye trapping agent, using elemental analysis and nuclear-magnetism The grafting rate of resonance measure vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium is 19%.
In the present embodiment, environmentally friendly anionic dye trapping agent is applied to anionic dye waste water processing
Take 500 parts containing 40 mg/L methyl reds, 4mg/L Pb2+Ion and 0.4mg/L citric acid waste water from dyestuff, add 0.6 part Environmentally friendly anionic dye trapping agent, stir 3 minutes under room temperature, with 0.1 mol/L salt acid for adjusting pH to 4, add 0.06 part of iron chloride, the flco precipitation for generating that particle diameter is more than 450 μm in 1 minute, 5 seconds is stirred under room temperature.After filtering, use Ultraviolet specrophotometer and atomic absorption spectrophotometer measure methyl red concentration are 0.048 mg/L and Pb2+Ion concentration is 0.02mg/L, removal efficiency>99%.
Example IV
It is a kind of environmentally friendly anionic dye trapping agent, and preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
5 parts of konjaku glucomannans (KGM) are added into 200 parts of water, 68 DEG C of temperature control, carry out dissolving 1 it is small when；Protected in nitrogen Under, initiator azo diisobutyl amidine hydrochloride V-50,20 parts of the diethylaminoethyl methacrylate of 1 part of addition (DAEMA) and 15 parts of N- vinyl formamides (NVF), when graft copolymerization 20 is small, cooling stops reaction；Add 200 parts of second Alcohol carries out precipitation separation, after filtering and drying, obtains high-purity konjaku glucomannan-grafting-poly- (methacrylic acid lignocaine Ethyl ester-random-N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r-NVF))；Using elemental analysis and nuclear magnetic resonance The grafting rate of Instrumental Analysis measure diethylaminoethyl methacrylate is that 95%, N- vinyl formamides grafting rate is 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, when reaction 40 is small, ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride is obtained；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
5 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 180 parts of 60 DEG C of water control temperature, when dissolving 2 is small under mechanical stirring； 10 parts of potassium hydroxide is added, when hydrolysis 48 is small, obtains konjaku glucomannan-grafting-poly- (methacrylic acid lignocaine Ethyl ester-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 30 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) When dianhydride (EGTAD), vinylamine and small ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acylation reaction 48, konjak portuguese gansu polyose is obtained Sugar-grafting-poly- (diethylaminoethyl methacrylate-random-vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium) (KGM- G-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anionic dye trapping agent, surveyed using elemental analysis and nuclear magnetic resonance The grafting rate for determining vinylamine ethyl glycol ethyl ether diaminetetraacetic acid sodium is 35%.
In the present embodiment, environmentally friendly anionic dye trapping agent is applied to anionic dye waste water processing
Take 1000 parts containing 40 mg/L are directly yellow, 5 mg/L Ni2+Ion and 0.6 mg/L citric acid waste water from dyestuff, add 1 part Environmentally friendly anionic dye trapping agent, stir 1 minute under room temperature, with 0.1 mol/L salt acid for adjusting pH to 5, add 0.1 part of frerrous chloride, the flco precipitation for generating that particle diameter is more than 600 μm in 1 minute, 2 seconds is stirred under room temperature, after filtering, is adopted It is 0.056 mg/L and Ni with ultraviolet specrophotometer and the directly yellow concentration of atomic absorption spectrophotometer measure2+Ion concentration is 0.02mg/L, removal efficiency>99%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from 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 anionic dye trapping agent, it is characterised in that the konjaku glucomannan including 1~5 part, 5~20 Part diethylaminoethyl methacrylate (DAEMA), 1~15 part of N- vinyl formamides (NVF), 50~200 parts of water, 0.1~1 part of water soluble starter azo diisobutyl amidine hydrochloride V-50,1~10 part of potassium hydroxide and 1~30 part of second Glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD)；They are mass fraction.
2. a kind of preparation method of environmentally friendly anionic dye trapping agent, it is characterised in that preparation process is as follows：
The synthesis of step 1 KGM-g-P (DAEMA-r-NVF)
By 1~5 part of konjaku glucomannan (KGM), the water of 50~200 parts of addition, 40~70 DEG C of temperature control, carries 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 Diethylaminoethyl acrylate (DAEMA) and 1~15 part of N- vinyl formamides (NVF), when graft copolymerization 1~20 is small, drop Temperature stops reaction；Add 50~200 parts of ethanol and carry out precipitation separation, after filtering and drying, obtain high-purity konjak portuguese gansu polyose Sugar-grafting-poly- (diethylaminoethyl methacrylate-random-N- vinyl formamides) copolymer (KGM-g-P (DAEMA-r- NVF)), wherein g represents 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, when reaction 20~40 is small are controlled in, obtains ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride；They are Mass fraction；
The synthesis of step 3 KGM-g-P (DAEMA-r-VAEGTANa)
1~5 part of KGM-g-P (DAEMA-r-NVF) is taken, adds 50~200 parts of water, 50~80 DEG C of temperature control, in mechanical agitation It is lower dissolving 1~2 it is small when；1~10 part of potassium hydroxide is added, when hydrolysis 12~48 is small, acquisition konjaku glucomannan-connect Branch-poly- (diethylaminoethyl methacrylate-random-vinylamine) copolymer KGM-g-P (DAEMA-r-VA)；Add 1~ 30 parts of ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride (EGTAD), vinylamine and ethylene glycol diethyl ether ethylenediamine tetraacetic acid (EDTA) dianhydride acyl When glycosylation reaction 12~48 is small, konjaku glucomannan-grafting-poly- (diethylaminoethyl methacrylate-random-ethene is obtained Amido ethylene glycol diethyl ether sodium ethylene diamine tetracetate) (KGM-g-P (DAEMA-r-VAEGTANa)) i.e. environmentally friendly anion Dyestuff trapping agent；They are mass fraction.
3. the preparation method of environmentally friendly anionic dye trapping agent according to claim 2, it is characterised in that described The grafting rate of diethylaminoethyl methacrylate (DAEMA) is 5~100%, vinylamine ethyl glycol ethyl ether diaminetetraacetic acid The grafting rate of sodium (VAEGTANa) is 1~50%.
4. a kind of application of environmentally friendly anionic dye trapping agent, it is characterised in that take 100~1000 parts of waste water, add 0.1~1 part of environmentally friendly anionic dye trapping agent, is stirred 1~5 minute under room temperature, adjusts pH to 2~5, cloudy in waste water Electrostatic Absorption, heavy metal in waste water occur for the DAEMA functional groups of ionic dye and environmentally friendly anionic dye trapping agent Chelant absorption occurs for the VAEGTANa functional groups of ion and environmentally friendly anionic dye trapping agent, anionic dye 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, is stirred 1 minute under room 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 functional groups, and flco of the particle diameter more than 100 μm is generated in 10 seconds and is precipitated, quickly Realize anionic dye and heavy metal ion separation of solid and liquid, water outlet is substantially colorless, reaches discharging standards.
5. the application of environmentally friendly anionic dye 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.
CN201711127657.4A 2017-11-15 2017-11-15 Environmentally friendly anionic dye trapping agent and preparation method thereof and its application Withdrawn CN107915804A (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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