CN107698006A - Environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent and preparation method and application - Google Patents
Environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent and preparation method and application Download PDFInfo
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- CN107698006A CN107698006A CN201711128655.7A CN201711128655A CN107698006A CN 107698006 A CN107698006 A CN 107698006A CN 201711128655 A CN201711128655 A CN 201711128655A CN 107698006 A CN107698006 A CN 107698006A
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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
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a kind of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent and preparation method and application, feature is by konjaku glucomannan, water, initiator azo diisobutyl amidine hydrochloride V 50, diethylaminoethyl methacrylate, N vinyl formamides, 1, 2 1,2-diaminocyclohexane tetraacetic acid dianhydrides, potassium hydroxide and carbon disulfide prepare environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, and the waste water for being used to handle the anionic dyes waste water given off in Dyestuff synthesis or dyeing and finishing process and the discharge of art coatings industry by environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent.It has trapping ability strong, sinking speed is fast, can handle low concentration solvay-type heavy metal ion, and anionic dye molecule and solvay-type heavy metal ion can be captured within the several seconds, fast-growth is into big sedimented particle, the purpose of quick separating anionic dye and heavy metal ion is realized, it is nontoxic, environmentally friendly, it is degradable, secondary pollution is not easily caused in use, easy to operate, processing cost is low, the advantages that strong adaptability.
Description
Technical field
The invention belongs to biological material and field of waste water treatment, and in particular to a kind of environmentally friendly konjaku glucomannan
Base anionic dye capturing settling agent and preparation method and application, its moon mainly given off in Dyestuff synthesis or dyeing and finishing process
Applied in ionic dyes waste water and 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 to provide a kind of environmentally friendly konjak portuguese gansu polyose glycosyl cloudy
Ionic dye capturing settling agent and preparation method thereof, trapping ability is strong, and sinking speed is fast, can handle low concentration solvay-type heavy metal
Ion, can capture anionic dye molecule and solvay-type heavy metal ion within the several seconds, and fast-growth is real into big sedimented particle
The purpose of existing quick separating anionic dye and heavy metal ion, it is nontoxic, environmentally friendly, it is degradable, do not easily cause in use
Secondary pollution, easy to operate, processing cost is low, strong adaptability.
In order to realize the purpose of the present invention, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye of the invention capture is sunk
The technical scheme of depressant prescription, which is achieved in that, is characterized in that the konjaku glucomannan for including 1~5 part（KGM）, 50~400 parts
Water, 0.1~1 part of initiator azo diisobutyl amidine hydrochloride V-50,5~40 parts of diethylaminoethyl methacrylate
（DAEMA）, 1~10 part of N- vinyl formamides（NVF）, 1~10 part 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA), 1
~10 parts of potassium hydroxide and 1~10 part of carbon disulfide；They are mass fractions.
In order to realize the purpose of the present invention, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye of the invention capture is sunk
The technical scheme of the preparation method of depressant prescription, which is achieved in that, is characterized in that preparation process is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
Take 1~5 part of konjaku glucomannan（KGM）, the water of 50~400 parts of addition, 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, 5~40 parts of methyl
Diethylaminoethyl acrylate（DAEMA）With 1~10 part of N- vinyl formamides（NVF）, graft copolymerization 1~20 hour, drop
Temperature stops reaction；After the ethanol of 50~400 parts of addition carries out precipitation separation, filtering and dried, high-purity konjak portuguese gansu polyose is obtained
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 fractions；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
20~40 parts of CDTA and 20~40 parts of acetic anhydride are dissolved in 20~40 parts of pyridine, controlled
Temperature is reacted 20~40 hours in 50~70 DEG C, obtains CDTA dianhydride；They are mass fractions；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
1~5 part of KGM-g-P (DAEMA-r-NVF) is taken, adds 50~400 parts of water, 50~80 DEG C of temperature control, in mechanical agitation
Lower dissolving 1~2 hour；Add 1~10 part of potassium hydroxide, hydrolysis 12~48 hours, acquisition konjaku glucomannan-connect
Branch-poly-（Diethylaminoethyl methacrylate-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 1~
10 parts of CDTA dianhydride (CDTA), acylation reaction 5~12 hours, acylation degree scope control 50~
99%, acquisition konjaku glucomannan-grafting-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene diamine tetrem
Sour sodium-random-vinylamine）（KGM-g-P(DAEMA-r-VACDTANa-r-VA )）；1~10 part of carbon disulfide is added, is controlled
Temperature carries out addition reaction 1~3 hour in 20~40 DEG C, obtains water-soluble konjaku glucomannan-grafting-poly-（Methacrylic acid two
Ethylamino ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-ethene amido nabam）Copolymer
（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）I.e. environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capture
Sedimentation agent；They are mass fractions.
In the technical program, the diethylaminoethyl methacrylate（DAEMA）Grafting rate be 5~100%, second
The grafting rate of enamine basic ring hexamethylene tetraacetic acid sodium (VACDTANa) is 1~20%, ethene amido nabam
(VACS2Na grafting rate) is 1~5%.
In order to realize the purpose of the present invention, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye of the invention capture is sunk
The technical scheme of the application of depressant prescription, which is achieved in that, is characterized in that the waste water for taking 100~1000 parts, adds 0.1~1 part
Environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, stir 1~5 minute under normal temperature, adjust pH to 2~5,
The DAEMA functional groups of anionic dye and environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent in waste water
Generation Electrostatic Absorption, heavy metal ions in wastewater and environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent
Chelant absorption occurs for VACDTANa functional groups, and anionic dye and heavy metal ion will be adsorbed in konjaku glucomannan completely and be total to
On polymers macromolecular scaffold；Add 0.01~0.1 part of the sedimentation agent that helps, stirred 1 minute under normal temperature, help the metal of sedimentation agent from
Son by quickly with the nabam on konjak portuguese gansu polyose sugar copolymer（-CS2Na）Generation chemical precipitation is reacted, 10 seconds
Interior flco of the generation particle diameter more than 100 μm precipitates, and quickly realizes anionic dye and heavy metal ion separation of solid and liquid, goes out water base
This is colourless, reaches 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 multi-functional, can make by electrostatic
Heavy metal ion is chelated on konjaku glucomannan molecular skeleton with quick anionic dyes and the chelation of catching, and can
The nabam being grafted by konjaku glucomannan molecular skeleton is with helping precipitating reagent metal ion that chelant quickly occurs
Precipitation reaction, big aggregation is generated within the several seconds, so as to realize rapid subsidence；
2nd, solve conventional synthesis series polymeric flocculant not problem of easy degradation, it is nontoxic, environmentally friendly, it is degradable after discarding, make
Secondary pollution is not easily caused during.
3rd, prepared by the present invention and use technique is simple, and caused sludge quantity is few, and processing cost is low.
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 konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, and preparation method is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
1 part of konjaku glucomannan（KGM）, 150 parts of water is added, temperature control carries out dissolving 0.5 hour in 45 DEG C；Protected in nitrogen
Under shield, initiator azo diisobutyl amidine hydrochloride V-50,8 parts of the diethylaminoethyl methacrylate of 0.1 part of addition
（DAEMA）With 3 parts of N- vinyl formamides（NVF）, graft copolymerization 2 hours, cooling stopping reaction；Add 150 parts of ethanol
After carrying out precipitation separation, filtering and drying, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid lignocaine second
Ester-random-N- vinyl formamides）Copolymer (KGM-g-P (DAEMA-r-NVF))；Using elementary analysis and NMR
The grafting rate of device analysis measure diethylaminoethyl methacrylate is that 23%, N- vinyl formamides grafting rate is 6%；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
20 parts of CDTA and 20 parts of acetic anhydride are dissolved in 20 parts of pyridine, temperature control is in 50 DEG C, instead
Answer 20 hours, obtain CDTA dianhydride；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
1 part of KGM-g-P (DAEMA-r-NVF) is taken, adds 50 parts of water, temperature control dissolves 1 hour under mechanical stirring in 50 DEG C；
Add 2 parts of potassium hydroxide, hydrolysis 12 hours, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid lignocaine
Ethyl ester-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 3 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides
(CDTA), acylation reaction 5 hours, acylation degree 87.5%, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid diethyl
Amino ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-vinylamine）（KGM-g-P(DAEMA-r-VACDTANa-
r-VA )）；2 parts of carbon disulfide is added, temperature control carries out addition reaction 1 hour, acquisition konjaku glucomannan-connect in 20 DEG C
Branch-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-sulphur of ethene amido two
For carbamic acid sodium）Copolymer（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）I.e. environmentally friendly Amorphophallus rivieri glucomannan
Glycan base anionic dye capturing settling agent；Using elementary analysis and nuclear magnetic resonance measuring copolymer ethylene amido cyclohexanediamine four
The grafting rate of sodium acetate is 7% and the grafting rate of ethene amido nabam is 1%.
In the present embodiment, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent is applied to anion
Dye waste water treatment method
100 parts are taken to contain 50 mg/L reactive brilliant reds（K-2BP）Waste water from dyestuff, add 0.1 part of environmentally friendly konjak portuguese gansu polyose
Glycosyl anionic dye capturing settling agent, stir 1 minute under normal temperature, with 0.1mol/L salt acid for adjusting pH to 2, add 0.01 part
Calcium chloride, the flco precipitation for generating that particle diameter is more than 130 μm in 1 minute, 10 seconds is stirred under normal temperature.After filtering, use is ultraviolet
Spectrophotometric determination reactive brilliant red concentration is 0.073 mg/L, removal efficiency>99%.
Embodiment two
It is a kind of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, and preparation method is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
Take 2 parts of konjaku glucomannan（KGM）, 250 parts of water is added, temperature control carries out dissolving 0.7 hour in 50 DEG C；In nitrogen
Under protection, initiator azo diisobutyl amidine hydrochloride V-50,20 parts of the diethylaminoethyl methacrylate of 0.4 part of addition
（DAEMA）With 6 parts of N- vinyl formamides（NVF）, graft copolymerization 6 hours, cooling stopping reaction；Add 250 parts of ethanol
After carrying out precipitation separation, filtering and drying, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid lignocaine second
Ester-random-N- vinyl formamides）Copolymer (KGM-g-P (DAEMA-r-NVF))；Using elementary analysis and NMR
The grafting rate of device analysis measure diethylaminoethyl methacrylate is that 48%, N- vinyl formamides grafting rate is 10%；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
25 parts of CDTA and 25 parts of acetic anhydride are dissolved in 25 parts of pyridine, temperature control is in 60 DEG C, instead
Answer 30 hours, obtain CDTA dianhydride；They are mass fractions；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
2 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 150 parts of water, temperature control dissolves 1.5 under mechanical stirring in 60 DEG C
Hour；Add 5 parts of potassium hydroxide, hydrolysis 24 hours, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid diethyl
Amino ethyl ester-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 6 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acids
Dianhydride (CDTA), acylation reaction 7 hours, acylation degree 80%, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid two
Ethylamino ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-vinylamine）（KGM-g-P(DAEMA-r-
VACDTANa-r-VA )）；4 parts of carbon disulfide is added, temperature control carries out addition reaction 2 hours in 30 DEG C, obtains konjaku Portugal
Sweet glycan-grafting-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-ethene
Amido nabam）Copolymer（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）It is i.e. environmentally friendly
Konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent；Using elementary analysis and nuclear magnetic resonance measuring copolymer ethylene amido ring
The grafting rate of hexamethylene tetraacetic acid sodium is 8% and the grafting rate of ethene amido nabam is 2%.
In the present embodiment, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent is applied to anion
Dye waste water treatment method
Take 300 parts containing 50 mg/L Acid Light Yellow Gs, 2 mg/L Cd2+Ion and 0.5 mg/L citric acid waste water from dyestuff, add
0.3 part of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, stir 1 minute under normal temperature, use 0.1mol/
L salt acid for adjusting pH adds 0.04 part of magnesium chloride to 3, and it is more than 160 μm to be stirred under normal temperature and particle diameter is generated in 1 minute, 7 seconds
Flco precipitation.After filtering, ultraviolet specrophotometer measure Acid Light Yellow G concentration is used to be inhaled for 0.045 mg/L and using atom
Receive spectrophotometric determination Cd2+Ion concentration is 0.06 mg/L, removal efficiency>99%.
Embodiment three
It is a kind of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, and preparation method is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
4 parts of konjaku glucomannan（KGM）, 350 parts of water is added, temperature control carries out dissolving 0.7 hour in 60 DEG C；Protected in nitrogen
Under shield, initiator azo diisobutyl amidine hydrochloride V-50,30 parts of the diethylaminoethyl methacrylate of 0.7 part of addition
（DAEMA）With 8 parts of N- vinyl formamides（NVF）, graft copolymerization 15 hours, cooling stopping reaction；Add 350 parts of ethanol
After carrying out precipitation separation, filtering and drying, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid lignocaine second
Ester-random-N- vinyl formamides）Copolymer (KGM-g-P (DAEMA-r-NVF))；Using elementary analysis and NMR
The grafting rate of device analysis measure diethylaminoethyl methacrylate is that 75%, N- vinyl formamides grafting rate is 16%；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
35 parts of CDTA and 35 parts of acetic anhydride are dissolved in 35 parts of pyridine, temperature control is in 65 DEG C, instead
Answer 35 hours, obtain CDTA dianhydride；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
3 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 300 parts of water, temperature control dissolves 1.8 under mechanical stirring in 60 DEG C
Hour；Add 7 parts of potassium hydroxide, hydrolysis 36 hours, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid diethyl
Amino ethyl ester-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 8 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acids
Dianhydride (CDTA), acylation reaction 9 hours, acylation degree 86%, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid two
Ethylamino ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-vinylamine）（KGM-g-P(DAEMA-r-
VACDTANa-r-VA )）；6 parts of carbon disulfide is added, temperature control carries out addition reaction 2.5 hours in 35 DEG C, obtains konjaku
Glucomannan-grafting-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-second
Enamine base nabam）Copolymer（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）It is i.e. environment-friendly
Type konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent；Using elementary analysis and nuclear magnetic resonance measuring copolymer ethylene amido
The grafting rate of 1,2-diaminocyclohexane tetraacetic acid sodium is 13% and the grafting rate of ethene amido nabam is 3%.
In the present embodiment, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent is applied to anion
Dye waste water treatment method
Take 500 parts containing 50 mg/L methyl reds, 2 mg/L Pb2+Ion and 0.5 mg/L citric acid waste water from dyestuff, add 0.5
Part environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, stir 3 minutes under normal temperature, with 0.1mol/L salt
Acid for adjusting pH adds 0.06 part of frerrous chloride to 4, and it is more than 330 μm to be stirred under normal temperature and particle diameter is generated in 1 minute, 4 seconds
Flco precipitates.After filtering, ultraviolet specrophotometer measure methyl red concentration is used for 0.038 mg/L and using Atomic absorption point
Light photometer Pb2+Ion concentration is 0.04mg/L, removal efficiency>99%.
Example IV
It is a kind of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, and preparation method is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
Take 5 parts of konjaku glucomannan（KGM）, 400 parts of water is added, temperature control carries out dissolving 1 hour in 70 DEG C；Protected in nitrogen
Under shield, initiator azo diisobutyl amidine hydrochloride V-50,40 parts of the diethylaminoethyl methacrylate of 1 part of addition
（DAEMA）With 10 parts of N- vinyl formamides（NVF）, graft copolymerization 20 hours, cooling stopping reaction；Add 400 parts of second
After alcohol carries out precipitation separation, filtering and dried, high-purity konjaku glucomannan-grafting-poly- is obtained（Methacrylic acid lignocaine
Ethyl ester-random-N- vinyl formamides）Copolymer (KGM-g-P (DAEMA-r-NVF))；Using elementary analysis and nuclear magnetic resonance
The grafting rate of Instrumental Analysis measure diethylaminoethyl methacrylate is that 95%, N- vinyl formamides grafting rate is 19%；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
40 parts of CDTA and 40 parts of acetic anhydride are dissolved in 40 parts of pyridine, temperature control is in 70 DEG C, instead
Answer 40 hours, obtain CDTA dianhydride；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
5 parts of KGM-g-P (DAEMA-r-NVF) is taken, adds 400 parts of 60 DEG C of water control temperature, is dissolved 2 hours under mechanical stirring；
Add 10 parts of potassium hydroxide, hydrolysis 48 hours, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid lignocaine
Ethyl ester-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 10 parts of 1,2- 1,2-diaminocyclohexane tetraacetic acid dianhydrides
(CDTA), acylation reaction 5 hours, acylation degree 73%, acquisition konjaku glucomannan-grafting-poly-（Methacrylic acid diethylamino
Base ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-vinylamine）（KGM-g-P(DAEMA-r-VACDTANa-r-
VA )）；10 parts of carbon disulfide is added, temperature control carries out addition reaction 3 hours, acquisition konjaku glucomannan-connect in 40 DEG C
Branch-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-sulphur of ethene amido two
For carbamic acid sodium）Copolymer（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）I.e. environmentally friendly Amorphophallus rivieri glucomannan
Glycan base anionic dye capturing settling agent；Using elementary analysis and nuclear magnetic resonance measuring copolymer ethylene amido cyclohexanediamine four
The grafting rate of sodium acetate is 14% and the grafting rate of ethene amido nabam is 5%.
In the present embodiment, environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent is applied to anion
Dye waste water treatment method
Take 1000 parts containing 50 mg/L are directly yellow, 2 mg/L Ni2+Ion and 1 mg/L citric acid waste water from dyestuff, add 1 part
Environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, stir 1 minute under normal temperature, adjusted with 0.1mol/L hydrochloric acid
PH to 5 is saved, adds 0.1 part of iron chloride, the flco that generation particle diameter is more than 200 μm in 1 minute, 2 seconds is stirred under normal temperature and is sunk
Form sediment.After filtering, ultraviolet specrophotometer measure directly yellow concentration is used for 0.042 mg/L and using atomic absorption spectrphotometry
Meter measure 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 konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, it is characterised in that including 1~5 part
Konjaku glucomannan（KGM）, 50~400 parts water, 0.1~1 part of initiator azo diisobutyl amidine hydrochloride V-50,5~
40 parts of diethylaminoethyl methacrylate（DAEMA）, 1~10 part of N- vinyl formamides（NVF）, 1~10 part 1,
2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA), 1~10 part of potassium hydroxide and 1~10 part of carbon disulfide；They are mass parts
Number.
A kind of 2. preparation method of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, it is characterised in that system
Standby step is as follows：
Step 1 KGM-g-P (DAEMA-r-NVF) synthesis
Take 1~5 part of konjaku glucomannan（KGM）, the water of 50~400 parts of addition, 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, 5~40 parts of methyl
Diethylaminoethyl acrylate（DAEMA）With 1~10 part of N- vinyl formamides（NVF）, graft copolymerization 1~20 hour, drop
Temperature stops reaction；After the ethanol of 50~400 parts of addition carries out precipitation separation, filtering and dried, high-purity konjak portuguese gansu polyose is obtained
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 fractions；
The synthesis of step 2 1,2- 1,2-diaminocyclohexane tetraacetic acids dianhydride (CDTA)
20~40 parts of CDTA and 20~40 parts of acetic anhydride are dissolved in 20~40 parts of pyridine, controlled
Temperature is reacted 20~40 hours in 50~70 DEG C, obtains CDTA dianhydride；They are mass fractions；
Step 3 KGM-g-P (DAEMA-r-VACDTANa-r-VACS2Na synthesis)
1~5 part of KGM-g-P (DAEMA-r-NVF) is taken, adds 50~400 parts of water, 50~80 DEG C of temperature control, in mechanical agitation
Lower dissolving 1~2 hour；Add 1~10 part of potassium hydroxide, hydrolysis 12~48 hours, acquisition konjaku glucomannan-connect
Branch-poly-（Diethylaminoethyl methacrylate-random-vinylamine）Copolymer KGM-g-P (DAEMA-r-VA)；Add 1~
10 parts of CDTA dianhydride (CDTA), acylation reaction 5~12 hours, acylation degree scope control 50~
99%, acquisition konjaku glucomannan-grafting-poly-（Diethylaminoethyl methacrylate-random-vinylamine basic ring hexamethylene diamine tetrem
Sour sodium-random-vinylamine）（KGM-g-P(DAEMA-r-VACDTANa-r-VA )）；1~10 part of carbon disulfide is added, is controlled
Temperature carries out addition reaction 1~3 hour in 20~40 DEG C, obtains water-soluble konjaku glucomannan-grafting-poly-（Methacrylic acid two
Ethylamino ethyl ester-random-vinylamine basic ring hexamethylene tetraacetic acid sodium-is random-ethene amido nabam）Copolymer
（KGM-g-P(DAEMA-r-VACDTANa-r-VACS2Na)）I.e. environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capture
Sedimentation agent；They are mass fractions.
3. the preparation side of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent according to claim 2
Method, it is characterised in that the diethylaminoethyl methacrylate（DAEMA）Grafting rate be 5~100%, vinylamine basic ring oneself
The grafting rate of sodium ethylene diamine tetracetate (VACDTANa) is 1~20%, ethene amido nabam (VACS2Connecing Na)
Branch rate is 1~5%.
4. a kind of application of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent, it is characterised in that take 100
~1000 parts of waste water, 0.1~1 part of environmentally friendly konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent is added, often
The lower stirring of temperature 1~5 minute, adjusts pH to 2~5, in waste water anionic dye and environmentally friendly konjak portuguese gansu polyose glycosyl the moon from
Electrostatic Absorption, heavy metal ions in wastewater and environmentally friendly konjaku occur for the DAEMA functional groups of sub- dyestuff capturing settling agent
Chelant absorption, anionic dye and a huge sum of money occur for the VACDTANa functional groups of glucose-mannitose polysaccharid anionic dye capturing settling agent
Category ion will be adsorbed on konjak portuguese gansu polyose sugar copolymer macromolecular scaffold completely；Add 0.01~0.1 part and help sedimentation agent,
Stirred 1 minute under normal temperature, help the metal ion of sedimentation agent by quickly with the dithiocarbamates first on konjak portuguese gansu polyose sugar copolymer
Sour sodium（-CS2Na）Generation chemical precipitation is reacted, and flco of the particle diameter more than 100 μm is generated in 10 seconds and is precipitated, it is quick realize it is cloudy 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 konjak portuguese gansu polyose glycosyl anionic dye capturing settling agent according to claim 4, its
Be characterised by it is described help sedimentation agent for calcium chloride, magnesium sulfate, frerrous chloride, ferric trichloride, alchlor it is one or two kinds of with
On any combination.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4432907A (en) * | 1979-09-10 | 1984-02-21 | Analytical Radiation Corporation | Diamine acid fluorescent chelates |
| 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 |
-
2017
- 2017-11-15 CN CN201711128655.7A patent/CN107698006A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4432907A (en) * | 1979-09-10 | 1984-02-21 | Analytical Radiation Corporation | Diamine acid fluorescent chelates |
| 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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