CN102861559A - Production method of polyacrylonitrile chelating resin metal adsorbent - Google Patents
Production method of polyacrylonitrile chelating resin metal adsorbent Download PDFInfo
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Abstract
The invention discloses a production method of a polyacrylonitrile chelating resin metal adsorbent. The method comprises the following steps of: (1) adding polyacrylonitrile microspheres to a reaction solvent for soaking; (2) adding 2-aminobenzothiazole as a ligand and metal sodium as a catalyst to a substance obtained in the step (1), stirring and reacting under the protection of nitrogen for 11-13h at the revolving speed of 200-300r/min and at 130-150 DEG C; and (3) soaking and washing the obtained modified polyacrylonitrile chelating resin with the reaction solvent until the washing liquid is colorless, then sequentially washing with de-ionized water, ethanol and ether for several times, washing with distilled water, then sequentially performing alkali washing, water washing, acid washing and water washing, and drying to constant weight at 40-60 DEG C so as to obtain the polyacrylonitrile chelating resin metal adsorbent.
Description
Technical field
The present invention relates to a kind of production method of Novel polypropylene nitrile chelating resin metal absorbent, be specifically related to a kind of heavy metal ion in the food to be had modification chelating resin material and the production method thereof that selective absorption, absorption property are good, can reuse.
Background technology
Life has can not bear it " weight ".Along with the industrialized development of each industry of China, the pollution problem of heavy metal has been the great problem of food security.But because the kind of heavy metal is many, concentration is low, the high complexity of sample and matrix interference are very serious, although a lot of sensitivity and selective very high Instrumental Analysis analysis had occurred in recent years, but expense is higher, be unfavorable for China most of middle-size and small-size food production or marketing enterprise, therefore comparatively economic spectrophotometer becomes the key instrument that heavy metal contaminants is measured.But general spectrophotometer detectability is higher, must to the heavy metal in the sample effectively separate in advance and and enrichment, thereby so that ageing, the sensitivity of AAS and selectively all improving a lot can reach the effect that compares favourably with the Other Instruments analytical method to a great extent fully.And chelating resin is a kind of separation and concentration material of function admirable, have that adsorption capacity is large, enrichment selectively better, easy and simple to handle, resin easily regenerate and the advantage such as acid and alkali-resistance, the aspects such as trace metal ion in the selective separation enrichment aqueous solution are used very extensive.
The Selective Separation that the polystyrene chelating resin is widely used in heavy metal ion reclaims, but has the shortcomings such as building-up process contaminated environment, eluting rate are low.The polyacrylonitrile chelating resin has good chemical stability, carry out Novel polypropylene nitrile chelating resin after the surface modification by addition reaction, when having the remarkable advantages such as atom utilization is high, non-environmental-pollution, will have better adsorption-desorption performance to multi-metal ion more.
Summary of the invention
The technical problem to be solved in the present invention provides the production method of a kind of technique polyacrylonitrile chelating resin adsorbent simple, with low cost, adopt the method production and Novel polypropylene nitrile chelating resin metal absorbent Hg (II) ion is had higher selective absorption.
In order to solve the problems of the technologies described above, the invention provides a kind of production method of polyacrylonitrile chelating resin metal absorbent, may further comprise the steps:
1., polyacrylonitrile microballoon (polyacrylonitrile based EVA) is added in the reaction dissolvent, soaked 20 ~ 28 hours, thereby after making the polyacrylonitrile microspheres swell up;
2., in step gains (the polyacrylonitrile microballoon after being swelling and remaining reaction dissolvent) 1., add as the 2-aminobenzothiazole (ABT) of part and add sodium metal as catalyst, under nitrogen protection in 130 ~ 150 ℃, with the rotating speed stirring reaction of 200 ~ 300 r/min 11 ~ 13 hours; After reaction finishes, filter, the filter cake of gained is the polyacrylonitrile chelating resin after the modification;
Polyacrylonitrile microballoon: 2-aminobenzothiazole (ABT): the weight ratio of sodium metal is 1:7 ~ 8:2 ~ 3;
3., be colourless with the polyacrylonitrile chelating resin after the modification with reaction dissolvent washing by soaking to cleaning solution, again successively with deionized water, ethanol, ether washing for several times, then wash with distilled water, then carry out successively alkali cleaning, washing, pickling and washing, be dried to constant weight under 40 ~ 60 ℃, get polyacrylonitrile chelating resin metal absorbent.
Improvement as the production method of polyacrylonitrile chelating resin metal absorbent of the present invention: 1. step is ethylene glycol (ED) with the reaction dissolvent of step in 3..
The present invention is take polyacrylonitrile microballoon (polyacrylonitrile based EVA) as parent, and 2-aminobenzothiazole (ABT) is part, and polyacrylonitrile microballoon (polyacrylonitrile based EVA) is carried out chemical modification, gets polyacrylonitrile chelating resin metal absorbent.
In the present invention:
Polyacrylonitrile microballoon (polyacrylonitrile based EVA) is selected D-160 type macroporous absorbent resin, for example can be available from Zhonglan Chenguang Chemical Inst.
Step 1. in, the polyacrylonitrile microballoon requires to be completely submerged in reaction dissolvent.For example, the reaction dissolvent of per 500 mg polyacrylonitrile microballoon adapteds, 300 ~ 500 mL.
Above-mentioned steps " carrying out successively alkali cleaning, washing, pickling and washing " in 3. is the routine operation mode, is: the gains of previous step are carried out first alkali cleaning (the NaOH solution of putting into concentration and be 1mol/L soaked 1 ~ 3 hour); Then be washed to cleaning solution for neutral; Carry out again pickling (it is that the HCl solution of 1mol/L soaked 1 ~ 3 hour that the gains after will washing are put into concentration); Then be washed to cleaning solution for neutral.
The present invention uses the infrared technique method, and synthetic Novel polypropylene nitrile chelating resin metal absorbent is carried out Structural Identification, inquires into response path and resin structure.Specific as follows:
1. the polyacrylonitrile microballoon (polyacrylonitrile based EVA) that takes a morsel mixes with KBr, and grinding, compressing tablet are measured its infrared spectrum, spectral region 4000 cm at the NICOLET-380 infrared spectrometer
-1~ 400 cm
-1, resolution ratio is 4 cm
-1, scanning times is 32 times.
2. measure respectively the polyacrylonitrile chelating resin metal absorbent of gained of the present invention and the infrared spectrum of part 2-aminobenzothiazole (ABT) according to the method for above-mentioned steps in 1..
3. pass through polyacrylonitrile microballoon, part and the comparative analysis of the infared spectrum of the Novel polypropylene nitrile chelating resin after synthesizing, infer the possible response path and the resin structure that the resin synthetic reaction.
The polyacrylonitrile chelating resin metal absorbent that adopts the inventive method production and get, carry out following experiment:
One, heavy metal ion adsorbed experiment:
Adsorption experiment carries out in constant temperature oscillator, the PAN-g-ABT(that accurately takes by weighing 4 parts a certain amount of (15.0 mg) is the polyacrylonitrile chelating resin metal absorbent of gained of the present invention) to the iodine flask of 100ml, add respectively certain volume (26 ml, 25 ml, 24 ml, 23 ml), the HAc-NaAc cushioning liquid of certain pH value (the pH value is 5.5) soaks 24h, then add respectively a certain amount of (4 ml, 5 ml, 6 ml, the heavy metal ion titer for preparing 7ml) under agitation carries out adsorption operations.Determination and analysis aqueous phase residual metal ion concentration at regular intervals is until balance.Calculate adsorbance (Q with following formula
e) and distribution ratio (D):
Q in the formula
eAdsorbance (the mgg of novel polyacrylonitrile chelating resin (PAN-g-ABT) during for balance
-1); C
oAnd C
eBe respectively the adsorption test GOLD FROM PLATING SOLUTION and belong to the initial concentration (mgmL of ion
-1) and equilibrium concentration (mgmL
-1); M is Novel polypropylene nitrile chelating resin quality (g); V is liquid phase volume (mL), refers to heavy metal ion titer and volume of buffer solution sum.
Two, desorption experiment
With the Novel polypropylene nitrile chelating resin adsorbent after the adsorption equilibrium with the deionized water cyclic washing repeatedly, blot the strippant that adds a certain amount of (30ml) behind the surface moisture with filter paper.Constant temperature oscillation is measured the concentration of heavy metal ion in the solution to the balance.The desorption efficiency E(% of adsorbent) is calculated as follows.
C in the formula
dEquilibrium concentration (mgmL for metal ion in the strippant
-1); V
dBe used stripping liquid volume (mL).C
oAnd C
eBe respectively the initial concentration (mgmL of aqueous phase metal ion
-1) and equilibrium concentration (mgmL
-1); V is liquid phase volume (mL).
The present invention has following advantage with respect to prior art:
1, the present invention produces Novel polypropylene nitrile chelating resin take polyacrylonitrile microballoon (PAN) as parent by addition reaction, has embodied preferably the feature of Green Chemistry: the atom utilization of raw material high (atom in the raw material is transformed in the product as much as possible); Not to or few in the environment the poisonous and hazardous accessory substance of discharging, have obvious economic benefit and environmental benefit.
2, the present invention utilizes chemical graft process that polyacrylonitrile is carried out modification, makes it have the characteristics such as mechanical strength is high, Heat stability is good, and metal ion is had good chelation.
3, the polyacrylonitrile chelating resin metal absorbent PAN-g-ABT that makes of the inventive method has stronger adsorption selectivity to Hg (II), adsorbance is large, adsorption rate is fast, and Ni (II), Cu (II), Zn (II), Cd (II), Pb (II) are seldom adsorbed or do not adsorb.
4, the Novel polypropylene nitrile chelating resin metal absorbent chemical stability that makes of the present invention is good, and easily wash-out (only needing a small amount of HCl solution just can reach complete wash-out) has more good regeneration and repeat performance, has reduced secondary pollution.
5, the production method of the Novel polypropylene nitrile chelating resin metal absorbent of the present invention's employing is simple, easy and simple to handle, and productive rate is high.
In sum, the present invention is first take polyacrylonitrile microballoon (PAN) as parent, select and contain N, S, the equiatomic organic ligand 2-of O aminobenzothiazole (ABT) to what heavy metal ion Hg (II) had a selective coordination ability, produce a kind of Novel polypropylene nitrile chelating resin metal absorbent by addition reaction, be applied in the selective separation enrichment of heavy metal Hg (II).Have not only with the synthetic polyacrylonitrile chelating resin of this method that mechanical strength is high, Heat stability is good; and metal ion Hg (II) had good chelation; adsorption capacity is large; repeat performance is good; and can improve resource utilization; reach protection of the environment, realize the purpose of sustainable development, have important Social benefit and economic benefit.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is PAN, the infrared spectrogram of ABT and PAN-g-ABT;
Fig. 2 is PAN-g-ABT resin synthetic route chart;
Fig. 3 be under the different pH values PAN-g-ABT to the metal biosorption Capacity Plan;
Fig. 4 be under the different temperatures PAN-g-ABT to the adsorpting rate curve figure of Hg (II);
Fig. 5 is that PAN-g-ABT is to the breakthrough curve figure of Hg (II);
Fig. 6 is that PAN-g-ABT is to the dynamic desorption curve map of Hg (II);
Fig. 7 is TGA analytic curve before and after the PAN-g-ABT absorption Hg (II).
The specific embodiment
Further describe the present invention below in conjunction with specific embodiment, but content of the present invention is not limited to this.
Remarks: the washing in following examples is with distilled water washs.
The production method of embodiment 1, polyacrylonitrile chelating resin metal absorbent may further comprise the steps:
1, take polyacrylonitrile microballoon (D-160 type macroporous absorbent resin) as parent, 2-aminobenzothiazole (ABT) is part, and the polyacrylonitrile microballoon is carried out chemical graft, carries out successively following steps:
1. take by weighing 500 mg polyacrylonitrile microballoons, move in the three-necked bottle of 500 mL, add the reaction dissolvent of 300 mL---in the ethylene glycol (ED), soaked overnight (namely soak 24 hours, thereby make the abundant swelling of polyacrylonitrile microballoon);
2., the part that in step gains (the polyacrylonitrile microballoon after being swelling and remaining ethylene glycol) 1., adds 3.57g---2-aminobenzothiazole (ABT), and a little catalyst---sodium metal (1240 mg), under nitrogen protection, in 140 ℃, add thermal agitation (rotating speed of 250r/min) reaction 12 hours; After reaction finishes, filter, get the polyacrylonitrile chelating resin after the modification;
3., with step 2. the polyacrylonitrile chelating resin after the modification of gained with reaction dissolvent--ethylene glycol (ED) is used reaction dissolvent after soaking 3 hours again--ethylene glycol (ED) washing of 50ml 3-4 time, until cleaning solution is colourless; Then wash successively with deionized water, ethanol, ether that (wash with deionized water first, the consumption of deionized water is 50ml/ time, washes 3 times; Then use absolute ethyl alcohol, the consumption of absolute ethyl alcohol is 50ml/ time, washes 3 times; Then wash with ether, the consumption of ether is 50ml/ time, washes 3 times), then with distilled water washing (50ml/ time, wash 3 times).Be the NaOH aqueous solution soaking 2 hours of 1mol/L with 50ml concentration again, be washed to neutrality; Be that the HCl solution of 1mol/L soaked 1 hour with 50ml concentration again, be washed to neutrality; At last 50 ℃ of lower vacuum drying to constant weight; Get polyacrylonitrile chelating resin metal absorbent (being PAN-g-ABT) 786mg.
2, use the infrared technique method, synthetic polyacrylonitrile chelating resin metal absorbent carried out Structural Identification, inquire into its response path and resin structure:
1. the polyacrylonitrile microballoon that takes a morsel mixes with KBr, and grinding, compressing tablet are measured its infrared spectrum, spectral region 4000 cm at the NICOLET-380 infrared spectrometer
-1~ 400 cm
-1, resolution ratio is 4 cm
-1, scanning times is 32 times.
2. measure respectively the infrared spectrum of polyacrylonitrile chelating resin metal absorbent and part 2-aminobenzothiazole (ABT) according to the method for above-mentioned steps in 1..
3. by the comparative analysis to the infared spectrum (see figure 1) of polyacrylonitrile microballoon, part and synthetic polyacrylonitrile chelating resin metal absorbent, infer the response path and the resin structure (see figure 2) that the resin synthetic reaction.
Experiment 1:
Accurately taking by weighing every part is 5 parts of the PAN-g-ABT of 15.0 mg, place 100 mL iodine flasks, after the HAc-NaAc cushioning liquid of pH=6.5, the pH=5.5 of corresponding adding 25ml, pH=4.5, pH=3.5, pH=2.5 soaks 24h respectively, heavy metal Hg (II) the ion mark liquid that adds the 2mg/mL of 5mL, place constant temperature oscillator under 25 ℃, with the rotating speed constant temperature jolting of 100 rpm, determination and analysis aqueous phase residual metal ion concentration at regular intervals is until balance.
As stated above, can obtain adsorbent to the adsorption capacity of different metal ion (being respectively 2mg/mL Ni (II), 2mg/mL Cu (II), 2mg/mL Zn (II), 2mg/mL Cd (II), 2mg/mL Pb (II)), thereby draw the impact that the polyacrylonitrile chelating resin of pH after on modification adsorbs each heavy metal ion performance.Acquired results as shown in Figure 3.
Experiment 2:
Accurately taking by weighing every part is PAN-g-ABT3 part of 30.0 mg, place 100 mL iodine flasks, add the HAc-NaAc cushioning liquid of 25ml optimal adsorption pH value=5.5, soak 24 h after the abundant swelling of resin, add 5mL, heavy metal Hg (II) the ion mark liquid of 2mg/mL, under 288 K, 298 K and 308 K, place constant temperature oscillation respectively, with the rotating speed constant temperature jolting of 100 rpm, determination and analysis aqueous phase residual metal ion concentration reaches balance until adsorb at regular intervals.With concentration of heavy metal ion (C
e) time (t) mapping is obtained adsorpting rate curve, acquired results is as shown in Figure 4.
Experiment 3:
Accurately taking by weighing every part is PAN-g-ABT5 part of 15.0 mg, place 100 mL iodine flasks, move into the HAc-NaAc cushioning liquid of 25 mL optimal adsorption pH value=5.5, soak 24 h after the abundant swelling of resin, move into 5 mL, heavy metal Hg (II) the ion mark liquid of 2mg/mL, under 25 ℃, place constant temperature oscillation, to adsorption equilibrium, measure the concentration (C of heavy metal ion in the solution with the rotating speed constant temperature oscillation of 100 rpm
e).Resin after the adsorption equilibrium is leached, after deionized water washing 3-4 time, dry, the HCl solution (0.5mol/L, 1mol/L, the 2mol/L that add 30 mL variable concentrations, 3mol/L, 4mol/L) 25 ℃, 100 rpm, constant temperature oscillation measure the concentration of heavy metal ion in the solution to the desorb balance again.Calculate desorption efficiency according to formula (3).When the result obtained carrying out desorb with 4mol/L HCl, desorption efficiency was 100%.
Experiment 4:
Accurately take by weighing 100.0mg PAN-g-ABT, soaked 24 hours with the optimum N aAc-HAc cushioning liquid that adsorbs Hg (II) in the static experiment (being the pH=5.5 buffer solution), after the abundant swelling of resin, in Φ 3 mm that pack into * 300 mm glass chromatography columns.Hg (II) the metal ion titer that adds 2mg/mL flows through resin column with the speed of 0.10 mL/min, gets 25 mL colorimetric cylinder Fractional Collections effluxes, and the every pipe GOLD FROM PLATING SOLUTION of sequentially determining belongs to the concentration (C of ion
i), until C
e=C
0With C
e/ C
0To effluent volume (V) mapping, draw the Dynamic Adsorption breakthrough curve.Calculate the Dynamic Adsorption amount.As shown in Figure 5.The Dynamic Adsorption amount of metal ion Hg (II) is 470.2mg/g.
Experiment 5:
After the resin column absorption of Dynamic Adsorption experiment is saturated, with the deionized water rinsing resin column for several times, then flow through resin column with the best desorption condition that obtains in the static desorption experiment (being that strippant is the HCl solution of 4mol/L) with the speed of 0.10 mL/min, with 10mL colorimetric cylinder Fractional Collections efflux, to have collected five times, the Hg that at every turn records (II) concentration is respectively 3. 800mg/mL, 0. 900mg/mL, 0.000mg/mL, 0.000 mg/mL, 0.000 mg/mL.Specifically as shown in Figure 6.With the resin column after the desorb again with deionized water rinsing for several times, again be used for adsorption of metal ions, every kind of resin column carries out Dynamic Adsorption-desorption cycle process five times, research resin repeat performance.The results are shown in Table 1.
Table 1, polyacrylonitrile chelating resin adsorbent PAN-g-ABT are to the regeneration adsorbance of Hg (II)
This shows, polyacrylonitrile chelating resin adsorbent PAN-g-ABT has good regeneration and repeat performance.
Experiment 6:
Take by weighing accurately that resin (PAN-g-ABT-Hg) sample behind optimum N aAc-HAc cushioning liquid (being the pH=5.5 buffer solution) gained absorption Hg (II) ion is respectively 10.0 mg in resin (PAN-g-ABT) before the abundant dried absorption and the experiment 1, use plum Teller TGA/DSC1 type simultaneous thermal analysis instrument carries out thermogravimetric analysis.
Analysis condition: carrier gas: nitrogen; Carrier gas flux: 20 mL/min; Heating schedule: 20 ℃/min, start-stop temperature: 50 ℃ ~ 1000 ℃.Specifically as shown in Figure 7.Hence one can see that, and PAN-g-ABT has preferably heat endurance, and the operating temperature of resin can reach 300 ℃.
Comparative Examples 1,
Change the step of embodiment 1 step 1 part in 2. into 2-Aminothiazoline (ATAL), all the other are equal to embodiment 1.
The polyacrylonitrile chelating resin of gained is called polyacrylonitrile chelating resin A, is used for metal biosorption and resolves experiment according to the method for above-mentioned experiment, and the correction data of the polyacrylonitrile chelating resin metal absorbent PAN-g-ABT of itself and embodiment 1 gained is as shown in table 2.
The polyacrylonitrile resin that table 2, different ligands synthesize is to Hg (II) metal biosorption amount and desorption efficiency
Hence one can see that, and the saturated adsorption capacity of Resin A is respectively 204.1mg/g when best pH=5.5, and its adsorbance can not show a candle to the adsorption capacity of PAN-g-ABT of the present invention.The characteristics such as and elute effect is also not as good as PAN-g-ABT, illustrated that the fine chelating resin metal absorbent of polypropylene (PAN-g-ABT) that the present invention synthesizes has adsorption capacity large, and reproducibility is strong.
Comparative Examples 2,
With the step of embodiment 1 step 1 in 2. part---the consumption of 2-aminobenzothiazole (ABT) changes respectively 3.00g into, 4.00g, all the other are with embodiment 1.
The polyacrylonitrile chelating resin of gained makes respectively polyacrylonitrile chelating resin I, polyacrylonitrile chelating resin II into, carry out metal biosorption and resolve experiment according to above-mentioned experimental technique, the correction data of the polyacrylonitrile chelating resin metal absorbent PAN-g-ABT of itself and embodiment 1 gained is as shown in table 3.
The fine chelating resin of polypropylene that the part of table 3, different amounts synthesizes is to Hg (II) metal biosorption amount and desorption efficiency
Comparative Examples 3,
With embodiment 1 step 1(be step 1. with step 3.) in reaction dissolvent make into respectively: methyl-sulfoxide (DMSO), DMF (DMF), all the other are fully with the step 1 of embodiment 1.
Adopt Vario EL III type elemental analyser to measure the content of S element in the resin to 2 kinds of adsorbents of above-mentioned gained and the polyacrylonitrile chelating resin metal absorbent PAN-g-ABT of the present invention (embodiment 1) gained, inquire into different solvents to synthetic resin functional group content and the experiment of function base conversion ratio.The result is as shown in table 4 below:
Table 4, reaction dissolvent are on the impact of synthetic resin functional group content and function base conversion ratio
Learnt by table 4,2-aminobenzothiazole (ABT) optimum response solvent is ethylene glycol (ED), and its conversion ratio has reached 56.61%, and ethylene glycol also has water-soluble, for the post processings such as washing of resin bring convenience, thereby to select ethylene glycol be the reaction dissolvent of reaction system.
Comparative Examples 4,
With embodiment 1 step 1(step 2. 140 ℃ make respectively 80 ℃ of temperature into), and 100 ℃, 120 ℃, all the other are fully with the step 1 of embodiment 1.Inquire into reaction temperature to the impact of synthetic resin function base conversion ratio.
Generally speaking, when temperature was higher, the swellability of resin increased, and ligand molecular enters the speed of resin inside to be accelerated, and the probability increasing with the function radical reaction is conducive to the carrying out that reacts.This is tested selected solvent ED and has higher boiling point (197 ℃).The molten point of part ABT is 129 ℃.Therefore, consider the molten boiling point of reaction part and reaction dissolvent, the synthetic discussion temperature of the PAN-g-ABT that reacts in solvent ED is chosen in 80 ℃ ~ 140 ℃.Experimental result shows, the function base conversion ratio of polyacrylonitrile chelating resin raises with the rising of temperature, therefore determine that the optimum synthesising temperature of PAN-g-ABT polyacrylonitrile chelating resin is 140 ℃.
At last, it is also to be noted that, what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. the production method of polyacrylonitrile chelating resin metal absorbent is characterized in that may further comprise the steps:
1., the polyacrylonitrile microballoon is added in the reaction dissolvent, soaked 20 ~ 28 hours, thereby make the polyacrylonitrile microspheres swell up;
2., in step gains 1., add as the 2-aminobenzothiazole of part and add sodium metal as catalyst, under nitrogen protection in 130 ~ 150 ℃, with the rotating speed stirring reaction of 200 ~ 300 r/min 11 ~ 13 hours; After reaction finishes, filter, get the polyacrylonitrile chelating resin after the modification;
Described polyacrylonitrile microballoon: 2-aminobenzothiazole: the weight ratio of sodium metal is 1:7 ~ 8:2 ~ 3;
3., be colourless with the polyacrylonitrile chelating resin after the modification with reaction dissolvent washing by soaking to cleaning solution, again successively with deionized water, ethanol, ether washing for several times, then wash with distilled water, then carry out successively alkali cleaning, washing, pickling and washing, be dried to constant weight under 40 ~ 60 ℃, get polyacrylonitrile chelating resin metal absorbent.
2. the production method of polyacrylonitrile chelating resin metal absorbent according to claim 1 is characterized in that: 1. described step is ethylene glycol with the reaction dissolvent of step in 3..
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103301817A (en) * | 2013-05-03 | 2013-09-18 | 浙江工商大学 | Chelate fiber ABTF and synthetic method thereof |
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| CN108586648A (en) * | 2018-03-30 | 2018-09-28 | 浙江工商大学 | A kind of chelating resin and its preparation method and application |
| CN109603774A (en) * | 2018-11-19 | 2019-04-12 | 浙江工商大学 | 2- amino -2- thiazoline modified polyacrylonitrile chelate fibre and its preparation method and application |
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| CN112958056A (en) * | 2021-02-03 | 2021-06-15 | 中南大学 | Three-dimensional graphene oxide composite material and preparation method and application thereof |
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