CN103102472B - Synthesis and application of copolymer of 1% of DVB crosslinking skeleton of chloromethylate polystyrene resin and 1,4-naphthoquinone - Google Patents
Synthesis and application of copolymer of 1% of DVB crosslinking skeleton of chloromethylate polystyrene resin and 1,4-naphthoquinone Download PDFInfo
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- CN103102472B CN103102472B CN201310007311.6A CN201310007311A CN103102472B CN 103102472 B CN103102472 B CN 103102472B CN 201310007311 A CN201310007311 A CN 201310007311A CN 103102472 B CN103102472 B CN 103102472B
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Abstract
The invention discloses synthesis and an application of copolymer of 1% of DVB crosslinking skeleton of chloromethylate polystyrene resin and 1,4-naphthoquinone. A 1,4-naphthoquinone substituted chloromethylate polystyrene copolymer is synthetized from 1% of DVB crosslinking chloromethylate polystyrene resin and 1,4-naphthoquinone as initial materials. The synthesis is low in reaction temperature, and short in reaction time (2-4 hours); the degree of substitution can be up to over 52%; the improvement of catalytic action of the polymer is facilitated; and the copolymer disclosed by the invention is applied to the degradation of waste water containing nitrogen. The results show that the microbial denitrification process and the microbial degradation azo-dye process are accelerated.
Description
Technical field
The present invention relates to a kind of synthesizing progress method of multipolymer and the application in microorganism denitrification process and azoic dyestuff microbiological deterioration process thereof, be specifically related to synthesis and the application of chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone multipolymer.
Background technology
Along with socioeconomic fast development, the azo dye wastewater discharged in water body environment every year, nitrate wastewater are significantly increasing.Due to the serious harm that it causes ecotope and HUMAN HEALTH, become the subject under discussion of people's common concern.The domestic and international treatment process for above-mentioned waste water can be divided into physico-chemical process and the large class of biological process two at present.Due to biological process, to have technique relative to physico-chemical process simple, with low cost, promotes the feature such as easier and become the prefered method processing these waste water.But in biologically effective degrading waste water, the speed of pollutent is comparatively slow, and cause the hydraulic detention time of process longer, initial cost is higher, the speed therefore how improving biologically effective degradation of contaminant becomes one of hot issue of research at present.
Guo Jianbo etc. have carried out more deep research in raising microorganism denitrification process and azoic dyestuff microbiological deterioration process, it is disclose immobilization quinones in the patent of CN 102060379 B to accelerate the application in microorganism denitrification process at notification number, described quinones is 1,8-chloroanthraquinone, 1,5-dichloroanthraquinone or 1,4,5,8-tetrachloroanthraquinone, be water-insoluble quinones, be fixed by sodium alginate to embed method, solve the shortcoming that water-insoluble quinones substance easily runs off.Publication number be disclose in the patent of CN 102277590A a kind of prepare containing naphthoquinones or anthraquinone compounds function amboceptor method and accelerating the application in microbiological deterioration nitrogenous effluent, described naphthoquinones or anthraquinone compounds are the salt compounds of naphthoquinones or anthraquinone, naphthoquinones or anthraquinone compounds are formed polypyrrole functional amboceptor by electrochemical polymerization-doping techniques by this patent application, add the adhesivity between activated carbon felt, solve water-soluble naphthoquinones salt or anthraquinone salt compounds easily to run off and cause the problem of secondary pollution, and have studied naphthoquinones salt or anthraquinone salt compounds in the application accelerating microbiological deterioration nitrogenous effluent, but this patent application adopts the influence factor of electrochemical reaction more, be the reaction process of a very complicated multivariable control, reaction process is wayward, and this electrochemical method is applicable to the compound dissolving rear generation anions and canons.
To sum up, although existing patent solves the technical problem of non-water-soluble quinones monomer and the easily loss in microbiological deterioration nitrogenous effluent of water miscible quinones salt compound amboceptor exploratoryly, but it is easily broken to adopt alginate calcium to fix water-insoluble amboceptor, and polypyrrole functional amboceptor is applicable to the compound dissolving rear generation anions and canons; How being fixed and then studying its application in nitrogenous effluent for water-soluble quinone-type monomer is but a difficult problem.In prior art 1,4-naphthoquinones is as a kind of important chemical intermediate, be mainly used in the raw material of the fine chemical products such as synthetic dyestuff, agricultural chemicals, medicine, sterilant, rubber, sensitive materials, pigment dyestuff, thermal recording medium, also be used as the polymerization regulator of synthetic rubber and resin, its water miscible feature makes it be difficult to apply as catalyzer in microbiological deterioration; The multipolymer adopting the present invention to prepare is solving 1, while 4-naphthoquinones easily runs off, investigate it, at microorganism denitrification process and azoic dyestuff microbiological deterioration process, there is booster action, to breach in prior art 1, the category of 4-naphthoquinones Application Areas, has widened its range of application.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1, the synthesis of 4-naphthoquinones multipolymer and application, it is with water-soluble 1,4-naphthoquinones be monomer, with polymkeric substance generation copolyreaction, the multipolymer rhodia formed carries out embedding and forms immobilized spherule, solve water-soluble quinone-type monomer easily to run off in water, cause the technical barrier of secondary pollution, and be applied in microorganism denitrification process and azoic dyestuff microbiological deterioration process.
In order to solve the problems of the technologies described above, the technical scheme that the present invention takes is:
A synthetic method for chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone multipolymer, with 1,4-naphthoquinone monomer and chloromethylated polystyrene resin 1%DVB cross-linked scaffold for starting raw material, comprises the following steps in the method:
Steps A, take chloromethylated polystyrene resin 1%DVB cross-linked scaffold that mole number is x and add a certain amount of ethylene dichloride, make chloromethylated polystyrene resin 1%DVB cross-linked scaffold be swelled into spherical at 50 DEG C, then be warming up to 73 ~ 83 DEG C, add catalyzer zinc chloride;
Step B, take 1,4-naphthoquinone that mole number is y and dissolve with ethylene dichloride, then gradation drops in the system of steps A, at 73 ~ 83 DEG C of reaction 2 ~ 4h, is cooled to room temperature, filters, obtain the thick product of multipolymer; Wherein, the ratio of x and y is 1:3 ~ 2:1;
Step C, purification: take DMF as solvent, with apparatus,Soxhlet's, the thick product in step B purified, obtain refining multipolymer.
Preferably, in step B, temperature of reaction is 78 ~ 80 DEG C.Test proves, along with temperature raises, during as 83 DEG C, in the multipolymer of formation, the substitution value of the chlorine that 1,4-naphthoquinone replaces in chloromethylated polystyrene resin 1%DVB cross-linked scaffold does not raise, reduces on the contrary.
In step B, the mol ratio of chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone is 1:2 ~ 1:1.
The multipolymer of above-mentioned synthesis, purification is applied in the microbiological deterioration containing nitrate and azo dye wastewater, effectively can accelerates the process of microorganism denitrification process and microorganism to degrade azo dyestuff.
The beneficial effect adopting technique scheme to produce is:
(1) the present invention is with the crosslinked chloromethylated polystyrene resin and 1 of 1%DVB, 4-naphthoquinones is starting raw material synthesis a kind of 1, the chloromethylated polystyrene multipolymer that 4-naphthoquinones replaces, its temperature of reaction is low, the reaction times is short (2 ~ 4h), substitution value reaches more than 52%, be conducive to the katalysis improving multipolymer, reduce the processing cost of nitrogenous effluent;
(2) the present invention adopts DMF to purify, and its purification time is 2 ~ 4h, and the product purity after purification reaches more than 99.0%; Purification time shorter, technique is simple, be applicable to suitability for industrialized production, and the multipolymer obtained foreign ion in the application process of microbiological deterioration nitrate wastewater and azo dye wastewater pollutes little;
(3) test recycled proves: multipolymer rhodia prepared by the present invention carry out embedding formed fixing after, effective constituent not easily runs off; For the fixing of water-soluble quinone-type monomer, prevent secondary pollution from adding a kind of selection mode;
(4) in prior art 1,4-naphthoquinones is as a kind of important chemical intermediate, be mainly used in the raw material of the fine chemical products such as synthetic dyestuff, agricultural chemicals, medicine, sterilant, rubber, sensitive materials, pigment dyestuff, thermal recording medium, also be used as the polymerization regulator of synthetic rubber and resin, its water miscible feature makes it be difficult to apply as catalyzer in microbiological deterioration; The multipolymer adopting the present invention to prepare is solving 1, while 4-naphthoquinones easily runs off, investigate it, at microorganism denitrification process and azoic dyestuff microbiological deterioration process, there is booster action, to breach in prior art 1, the category of 4-naphthoquinones Application Areas, has widened its range of application.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of multipolymer, 1,4-naphthoquinone and the chloromethylated polystyrene resin 1%DVB cross-linked scaffold synthesized in embodiment 1, and wherein, a is multipolymer, b is 1,4-naphthoquinone, c is chloromethylated polystyrene resin 1%DVB cross-linked scaffold;
Fig. 2 is that multipolymer synthesized in embodiment 1 is accelerating the test effect figure in azoic dyestuff microbiological deterioration process, and wherein ■ representative only adds the concentration of Acid Red B in the waste water of Degradation of Azo Dyes microorganism and blank bead; ▲ representative adds the concentration of Acid Red B in the waste water of Degradation of Azo Dyes microorganism and immobilization skeleton bead; ● representative adds the concentration of Acid Red B in the waste water of Degradation of Azo Dyes microorganism and immobilization multipolymer bead;
Fig. 3 is that multipolymer synthesized in embodiment 1 is accelerating the circulation experiment design sketch in azoic dyestuff microbiological deterioration process, with the ratio containing the Acid Red B percent of decolourization of immobilized polymer system and the Acid Red B percent of decolourization of blank bead system for ordinate zou (degradation time 8h), experiment number is X-coordinate;
Fig. 4 is the accelerated test design sketch of different concns immobilization multipolymer azo dyes microbiological deterioration process in embodiment 1, and wherein ■ representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and blank bead; ● representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and the immobilization multipolymer bead containing 0.5g multipolymer; ▲ representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and the immobilization multipolymer bead containing 1g multipolymer; ★ representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and the immobilization multipolymer bead containing 1.5g multipolymer; Zero representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and the immobilization multipolymer bead containing 2g multipolymer; + representative adds Acid Red B concentration in the waste water of Degradation of Azo Dyes microorganism and the immobilization multipolymer containing 2.5g multipolymer;
Fig. 5 is the broad spectrum test effect figure of multipolymer catalysis azoic dyestuff microbiological deterioration synthesized in embodiment 1, and when being 80% with the dye decolored rate of immobilization copolymer systems, be ordinate zou with the ratio of blank bead system percent of decolourization, kind of dyes is X-coordinate;
Multipolymer synthesized in Fig. 6 embodiment 1 is to nitrate microorganism denitrification accelerated test design sketch, and wherein, ■ representative only adds the concentration of nitrate nitrogen in the nitrate wastewater of denitrifying microorganism and blank bead; ◆ representative adds the concentration of nitrate nitrogen in the nitrate wastewater of denitrifying microorganism and immobilization skeleton bead; ▲ representative adds the concentration of nitrate nitrogen in the nitrate wastewater of denitrifying microorganism and immobilization multipolymer bead;
Fig. 7 ~ Figure 10 is when 73 DEG C, 78 DEG C, 80 DEG C and 83 DEG C respectively, the relation curve between reaction times and pH.
Embodiment
In order to understand essence of the present invention better, the experimental result below by embodiment multipolymer illustrates its application in microorganism denitrification process and azoic dyestuff microbiological deterioration process.
embodiment 1
With 1,4-naphthoquinone monomer and chloromethylated polystyrene resin 1%DVB cross-linked scaffold for starting raw material, according to following step synthesis and purification multipolymer:
Steps A, take the chloromethylated polystyrene resin 1%DVB cross-linked scaffold of 0.036mol, added agitator, prolong, thermometer are installed 100mL tetra-mouthfuls of round bottom ground flasks in, then the ethylene dichloride of 20mL is added, setting thermostatic type heated and stirred actuator temperature is 50 DEG C, starts heated and stirred 10min, chloromethylated polystyrene resin 1%DVB cross-linked scaffold is made to be swelled into spherical, then above-mentioned system is warming up to 78 DEG C, adds 0.1g catalyzer zinc chloride;
Step B, take 1 of 0.036mol, 4-naphthoquinones also dissolves with 15mL ethylene dichloride, after 10min, divide with dropper and drop in the system of steps A three times, at 78 DEG C of reaction 3h, then room temperature is cooled to, vacuum filtration, and with using ethylene dichloride and distilled water flushing filter cake respectively, to remove remain in filter cake 1,4-naphthoquinones and zinc chloride, obtain the thick product of about 2g multipolymer;
Step C, purification: choose supporting apparatus,Soxhlet's and Florence flask, in Florence flask, add about its solvent is the DMF of 2/3, is placed on by thick for the multipolymer of about 2g product in filter paper cover, is positioned in extraction cell, with heating mantle heats; When after solvothermal boiling, utilize solvent refluxing and syphonic effect, make the solvend in thick product be enriched in flask, to reach the object of purifying substances; When the solution of condensing reflux in extraction cell is colourless (the purification time is about 2h), stop heating, filter paper is overlapped electric heating constant-temperature blowing drying box is put in taking-up, dry 6h removes solvent under 105 DEG C of conditions, obtain purified copolymers, preserve stand-by.
Through above-mentioned reaction, chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinones forms multipolymer, become non-water-soluble chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1, the multipolymer of 4-naphthoquinones, infrared analysis is carried out to this multipolymer, result as shown in Figure 1, as can be seen from the figure: wave number is 1670cm
-1-1680cm
-1place's (absorption peak of C=O), not there is absorption peak in chloromethylated polystyrene resin 1%DVB cross-linked scaffold, and 1, absorption peak has all been there is in 4-naphthoquinones and multipolymer at this place, this peak is the C=O bond in naphthoquinones, shows: 1,4-naphthoquinone successful polymerization on chloromethylated polystyrene resin 1%DVB cross-linked scaffold, its reaction mechanism is the chlorine that 1,4-naphthoquinone instead of on chloromethylated polystyrene resin 1%DVB cross-linked scaffold.
Ultimate analysis is carried out to the above-mentioned multipolymer of synthesis, and the substitution value calculating chlorine in chloromethylated polystyrene resin 1%DVB cross-linked scaffold is 53.9%.
Fix above-mentioned multipolymer with rhodia, make bead, and with blank bead and immobilization skeleton bead as Comparability test.
1, the making method of blank bead is as follows:
(1) 7g rhodia is taken in containing in the beaker of 60mL acetone soln, with the ultrasonic 30 ~ 60min of ultrasonic cleaning machine;
(2) beaker is taken out from cleanser be placed on magnetic stirring apparatus and stir, ultrasonic 20 ~ 30min; Add 5mL deionized water, 1.5g magnesium perchlorate and 0.5mL tween 80, ultrasonic 1 ~ 2h, shaking table vibration 1 ~ 2h;
(3) again through ultrasonic, stir and make it mix, then this mixed solution injector for medical purpose is clamp-oned paraffin and water volume ratio is in 3:1 liquid, forming diameter is the bead of 2 ~ 3mm, as experiment blank, makes blank bead.
2, the preparation method of immobilization skeleton bead:
Identical with the step of the blank bead of preparation, unlike also adding 2g chloromethylated polystyrene resin 1%DVB cross-linked scaffold (being called for short immobilization skeleton bead) in step (2).
3, the preparation method of immobilization multipolymer bead:
Identical with the step of the blank bead of preparation, unlike also adding multipolymer (being called for short immobilization multipolymer bead) in step (2).
Blank bead, immobilization skeleton bead and immobilization multipolymer bead are fed in identical nitrogenous effluent respectively the effect of multipolymer in microorganism denitrification process and microorganism to degrade azo dyestuff investigated the present embodiment and prepare below.
One, the application of multipolymer in microorganism to degrade azo dyestuff
Blank bead, immobilization skeleton bead and immobilization multipolymer bead (adding multipolymer prepared by 2g the present embodiment in the preparation process of this bead) are used normal saline flushing 3 times respectively, then 250mL is suspended in respectively containing in the 150mg/L Acid Red B waste water of logarithmic phase microorganism, carry out anaerobe decolouring, measure Acid Red B concentration over time, result as shown in Figure 2.
As can be seen from Figure 2: after 8h, add in the system of blank bead, the percent of decolourization of Acid Red B is 55.90%; Add in the system of immobilization skeleton bead, the percent of decolourization of Acid Red B is 61.15%; Add in the system of immobilization multipolymer bead, the percent of decolourization of Acid Red B is 93.35%.The Acid Red B percent of decolourization of immobilization multipolymer bead system is 1.67 times of blank reaction system, shows that multipolymer prepared by the present invention is conducive to accelerating the degradation process of azoic dyestuff microorganism.
The system of above-mentioned immobilization multipolymer bead is cycled to used in the degraded of azoic dyestuff, investigate it and recycle performance, result as shown in Figure 3.As can be seen from the figure: along with the increase of cycle index, the percent of decolourization of azoic dyestuff does not decline, and shows: (1) is recycling in process, co-polymer chemical stable in properties, and the phenomenon of chemical bond rupture, 1,4-naphthoquinone loss does not occur; (2) multipolymer synthesized and rhodia bonding force strong.
In the preparation of immobilization multipolymer bead, add 0.5,1.0,1.5 and the multipolymer prepared of 2g the present embodiment respectively, form the bead of different copolymer substrate concentration, then respectively the immobilization multipolymer bead of different concns is put into 250mL containing in the 150mg/L Acid Red B waste water of logarithmic phase microorganism, investigate the booster action of its different concns to Acid Red B, result as shown in Figure 4.As can be seen from the figure: the booster action of the multipolymer azo dyes microbiological deterioration of immobilization different concns is different, and along with the increase of multipolymer dosage, booster action is obvious.
The above-mentioned bead containing multipolymer is carried out the wide spectrum experiment of azoic dyestuff, result as shown in Figure 5, as can be seen from the figure: the multipolymer prepared by the present embodiment has booster action to following 6 kinds of azoic dyestuff bio anaerobics decolouring, shows that the booster action of multipolymer azo dyes microbiological deterioration has broad spectrum.
Two, multipolymer is accelerating the application in microorganism denitrification process
Blank bead, immobilization skeleton bead and immobilization multipolymer bead (adding multipolymer prepared by 2g the present embodiment in the preparation process of this bead) are used normal saline flushing 3 times respectively, is then suspended in 250mL respectively and carries out experimental study containing in the 200mg/L nitrate nitrogen waste water of logarithmic phase denitrifying microorganism.Measure nitrate nitrogen concentration over time, result as shown in Figure 6.
As can be seen from Figure 6: after 10h, add in the system of blank bead, the clearance of nitrate nitrogen is 61.62%; Add in the system of immobilization skeleton bead, the clearance of nitrate nitrogen is 67.32%; Add in the system of immobilization multipolymer bead, the clearance of nitrate nitrogen is 82.99%.The nitric acid nitrogen salt clearance of immobilization multipolymer bead is 1.35 times of blank bead system, shows that chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone multipolymer are conducive to accelerating the degradation process of denitrifying microorganism to nitrate.
embodiment 2 ~ embodiment 6
With reference to the step of embodiment 1, carry out synthesis and the purified reaction of multipolymer according to the parameter of following table.Other reaction parameter those skilled in the art adjust accordingly.
The reaction parameter of table 1 embodiment 1 ~ embodiment 6 and speedup effect
In each embodiment, Degradation of Azo Dyes and nitrate nitrogen degraded have all carried out round-robin test, and result shows: along with the increase of cycle index, and the percent of decolourization of azoic dyestuff and the clearance of nitrate nitrogen do not have considerable change.
embodiment 7
As different from Example 1, in the present embodiment, setting experiment temperature of reaction is respectively 70 DEG C, 73 DEG C, 78 DEG C, 80 DEG C, 83 DEG C.In the present invention, chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1, the reaction of 4-naphthoquinones produces hydrogen chloride gas, hydrogenchloride is insoluble to organic reaction system, hydrogen chloride gas is collected, is dissolved in 100mL distilled water, by measuring the pH value of this distilled water, the hydrionic concentration and then the degree of reflection replacement and the relation between temperature of reaction and substitution value that produce when reaction system reaches stable can be calculated.
Result shows: when temperature of reaction is 70 DEG C, and after 1h is carried out in reaction, the pH value of system does not change, and that is chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone do not react at 70 DEG C.73 DEG C, 78 DEG C, 80 DEG C, 83 DEG C time, in the identical timed interval (the present embodiment is 5min), the pH value of test reaction system, to react the relation curve between time and pH according to pH value, sees Fig. 7 ~ 10.Relational expression according between hydrogen ion concentration and pH: pH=-lg [H
+], hydrionic concentration when showing that system reaches stable under differing temps, in table 2.
Hydrionic concentration when stablizing under table 2 differing temps
As known from Table 2, when temperature of reaction is 78 DEG C, the reaction of 1,4-naphthoquinone and chloromethylated polystyrene resin 1%DVB cross-linked scaffold is more abundant.78 DEG C is this reaction preferably temperature of reaction.
To sum up, the present invention is by 1,4-naphthoquinones monomer and chloromethylated polystyrene resin 1%DVB cross-linked scaffold occur to replace copolyreaction, generate a kind of non-water-soluble quinones multipolymer, thus define a kind of new immobilized amboceptor, apply in microbiological deterioration for quinone-type monomer and open up a new way.
Claims (6)
1. a synthetic method for chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone multipolymer, with 1,4-naphthoquinone monomer and chloromethylated polystyrene resin 1%DVB cross-linked scaffold for starting raw material, is characterized in that comprising the following steps in the method:
Steps A, take mole number and be
chloromethylated polystyrene resin 1%DVB cross-linked scaffold and add a certain amount of ethylene dichloride, make chloromethylated polystyrene resin 1%DVB cross-linked scaffold be swelled into spherical at 50 DEG C, be then warming up to 73 ~ 83 DEG C, add catalyzer zinc chloride;
Step B, take mole number and be
1,4-naphthoquinone and with ethylene dichloride dissolve, then gradation drops in the system of steps A, 73 ~ 83 DEG C reaction 2 ~ 4h, be cooled to room temperature, filter, obtain the thick product of multipolymer; Wherein,
with
ratio be 1:3 ~ 2:1;
Step C, purification: take DMF as solvent, with apparatus,Soxhlet's, the thick product in step B purified, obtain refining multipolymer.
2. the synthetic method of chloromethylated polystyrene resin 1%DVB cross-linked scaffold according to claim 1 and 1,4-naphthoquinone multipolymer, is characterized in that in step B, temperature of reaction is 78 ~ 80 DEG C.
3. chloromethylated polystyrene resin 1%DVB cross-linked scaffold according to claim 1 and 1, the synthetic method of 4-naphthoquinones multipolymer, it is characterized in that the mol ratio of chloromethylated polystyrene resin 1%DVB cross-linked scaffold and 1,4-naphthoquinone in step B is 1:2 ~ 1:1.
4. the synthetic method of chloromethylated polystyrene resin 1%DVB cross-linked scaffold according to claim 1 and 1,4-naphthoquinone multipolymer, is characterized in that the filter cake filtering gained in step B respectively with ethylene dichloride and distilled water wash.
5. the synthetic method of chloromethylated polystyrene resin 1%DVB cross-linked scaffold according to claim 1 and 1,4-naphthoquinone multipolymer, the time that its feature is purified in step C is 2 ~ 4h.
6. the chloromethylated polystyrene resin 1%DVB cross-linked scaffold prepared by claim 1 and 1,4-naphthoquinone multipolymer are accelerating the application in microorganism denitrification process and microorganism to degrade azo dyestuff.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1002643A (en) * | 1960-12-22 | 1965-08-25 | Montedison Spa | New organic peroxides |
| US4843130A (en) * | 1987-04-17 | 1989-06-27 | Otsuka Kagaku Kabushiki Kaisha | Antibacterial polymer |
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| CN1062712C (en) * | 1997-08-29 | 2001-03-07 | 中国石油化工总公司 | Insoluble quaternary polyphosphate bactericidal agent and preparation thereof |
| CN100441297C (en) * | 2006-12-11 | 2008-12-10 | 南京大学 | Supported metal phthalocyanine photocatalyst and its preparing method |
| CN101590429A (en) * | 2008-05-30 | 2009-12-02 | 南开大学 | A kind of resin catalyst that utilizes visible light photocatalytic degradation of organic pollutants and preparation method thereof |
| CN101698699B (en) * | 2009-11-04 | 2013-06-19 | 大连理工大学 | Method for preparing macroporous polymer fixed quinonoid compound |
| CN102277590B (en) * | 2011-06-13 | 2013-07-31 | 河北科技大学 | Preparation method of polypyrrole functional mediator doped with water-soluble anthraquinone or naphthoquinone compound and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1002643A (en) * | 1960-12-22 | 1965-08-25 | Montedison Spa | New organic peroxides |
| US4843130A (en) * | 1987-04-17 | 1989-06-27 | Otsuka Kagaku Kabushiki Kaisha | Antibacterial polymer |
Non-Patent Citations (1)
| Title |
|---|
| Evaluation of the Characteristics of Microorganisms that Contribute to Denitrification in the Paddy Drainage Treatment Apparatus by Quinone Composition Measurement;Koji HAMADA et al;《Journal of Water and Environment Technology》;20101231;第8卷(第4期);第421-427页 * |
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