CN103223333B - Di-amidoxime group containing modified silica gel adsorbent and preparation method thereof - Google Patents
Di-amidoxime group containing modified silica gel adsorbent and preparation method thereof Download PDFInfo
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Abstract
Belonging to the field of modified silica gel adsorbents, the invention particularly relates to a di-amidoxime group containing modified silica gel adsorbent specific to heavy metal copper ions in an adsorption solution and a preparation method thereof. The preparation method includes: taking silica gel as a starting raw material, conducting activation by a methanesulfonic acid solution, performing impregnation in a toluene solution of KH550, carrying out drying, then adding the obtained dry particles into an N, N-dimethylformamide solution of acrylonitrile to undergo first modification, and carrying out a treatment, then adding the dried first modified particles into a mixed solution of a hydroxylamine hydrochloride solution and a sodium carbonate solution to perform second modification, and conducting a treatment, thus obtaining dried second modified particles, i.e. a di-amidoxime group containing modified silica gel adsorbent finished product. The di-amidoxime group involved in the invention can be chelated with a heavy metal, thus having a strong adsorption effect on heavy metal copper ions. And compared with single-oxime group adsorbents, the di-amidoxime group containing modified silica gel adsorbent disclosed in the invention has substantially improved adsorption performance on copper ions, and the adsorption capacity is increased to 30mg/g.
Description
Technical field
The invention belongs to modified silica-gel absorbent fields, particularly relate to the modified silica-gel adsorbent containing two amidoxime group and preparation method thereof for heavy metal copper ion in adsorbent solution.
Background technology
As everyone knows, along with the fast development of Chinese national economy, environmental pollution and derivative economy thereof and social concern manifest day by day.The protection of water environment, deterioration and administer the extensive concern, the particularly improvement of heavy metal polluted-water that also more and more cause various circles of society.Research and development utility model Treatment process is healthy and economical to fwaater resources protection, human life, social sustainable development has theory and practical significance.
In numerous heavy metal water body treatment technology, the adsorption and enrichment of heavy metal in water ion is simple because of method, operates the study hotspot that the many advantages such as simple and easy and removal efficiency height have become this respect theory and practical application.Superfine people is in " applied chemistry " in high, 2010,27(3): " graft type amidoxim resin/SiO that 313-316 delivers
2the preparation of function and service particulate " in a literary composition, adopt solution polymerization process, by acrylonitrile grafting on the silica gel particle through KH570 modification, after through amidoxim reaction, the obtained sorbing material containing amidoxime group.But still have the following disadvantages: 1. time of equilibrium adsorption is long; 2. not good to low-concentration heavy metal adsorption effect; 3. grafting degree is not high.Chinese patent CN101596449A, a kind of preparation method of amidoxime group uranium extraction sorbent, the titanium dioxide blending oximate that acrylonitrile powder and collosol and gel are prepared by this patent, obtained hydridization amidoxime group uranium extraction material, but still have the following disadvantages: 1. resulting materials mechanical strength is inadequate; 2. material is not high to the adsorbance of uranium; Chinese patent CN101357325A, a kind of globular cellulose chelate sorbent and preparation side-Fa thereof containing amidoxime group and carboxyl, this patent utilization acrylonitrile and Graft Copolymerization of Cellulose, by saponification, oximate, obtained a kind of globular cellulose chelate sorbing material containing amidoxime group and carboxyl, but still have the following disadvantages: 1. grafting degree is not high; 2. materials adsorption is selective not high; 3. material specific surface area causes not greatly adsorption effect not good.Chinese patent CN101954268A, a kind of preparation method of adsorbent of heavy metal ions in water, this patent utilization sulfhydryl compound modified nano-titanium dioxide, obtained a kind of nano titanium oxide sorbing material containing sulfydryl, but still have the following disadvantages: nanoscale sorbing material is not easily separated after using, and may cause secondary pollution.Pottery front yard first waits people in " chemical research and application ", 2003, the fiber containing amidoxime groups mentioned in " fiber containing amidoxime groups is to the adsorption dynamics adsorption kinetics of copper (II) " literary composition that 6:823-825 delivers is 9.8mg/g to the adsorbance of copper ion, still exists and waits deficiency to the adsorbance of copper ion is on the low side.
Not enough in order to overcome these, stable chemical nature, silica gel absorber that mechanical strength is high are carried out the modified silica-gel adsorbent that modification obtains containing two amidoxime group by the present invention, with the heavy metal copper ion in its absorption waste water.
Summary of the invention
the technical problem solved:the present invention overcomes the deficiencies in the prior art and proposes a kind of modified silica-gel adsorbent containing two amidoxime group and preparation method thereof, the present invention carries out modification to stable chemical nature, silica gel absorber that mechanical strength is high, obtain the modified silica-gel adsorbent containing two amidoxime group, because it contains two amidoxime group, heavy metal copper ion has stronger suction-operated, and compared with single amidoxime group, absorption property significantly improves.
technical scheme:the present invention adopts inorganic material silica gel and organic material acrylonitrile compound to prepare a kind of modified silica-gel adsorbent containing two amidoxime group, and its structural formula is:
According to a kind of modified silica-gel adsorbent containing two amidoxime group of the present invention, it is characterized in that being prepared by following steps and obtaining:
Step one, activation: 30g 100-200 object column chromatography silica gel is placed in the pyrovinic acid solution that 150mL volumetric concentration is 5%, condensing reflux at 90 DEG C Keep agitation 4 hours, reacted rear distilled water and repeated to rinse until cleaning solution is in neutral, and at 50 DEG C vacuum drying 24 hours;
Step 2, dipping: the activated silica gel that 10g step one obtains is joined in the toluene solution of 150mL KH550, wherein the volumetric concentration of KH550 is 10%, condensing reflux at 70 DEG C Keep agitation 24 hours, filter to obtain coarse granule, then be that extractant extracts 24 hours in apparatus,Soxhlet's with toluene, remove the unreacted KH550 of Silica Surface, obtain impregnated granules;
Step 3, dry: impregnated granules step 2 obtained vacuum drying 24 hours at 50 DEG C, obtains dried particles;
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide (DMF) solution, wherein acrylonitrile volumetric concentration is 15%, then nitrogen is passed into, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 65-85 DEG C Keep agitation 5 hours, filter after reaction and obtain a modified particles, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, condensing reflux at 70 DEG C Keep agitation 6 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
The preparation principle of the modified silica-gel adsorbent containing two amidoxime group of the present invention take silica gel as raw material, activate through methanesulfonic acid, after being washed till neutral oven dry and coupling agent KH550 (gamma-aminopropyl-triethoxy-silane) react, amino is linked silica gel particle surface, obtains modified particles KH550-SiO
2.Under the initiation of azodiisobutyronitrile, the double bond on acrylonitrile and modified particles KH550-SiO
2on amino polymerization, obtain AN-SiO
2.Finally, hydroxylamine hydrochloride and sodium carbonate react the azanol that discharges by AN-SiO
2cyano group in particle is converted into amidoxime group, thus obtains the modified silica-gel adsorbent A O-SiO containing two amidoxime group
2.
beneficial effect:compared with prior art, mechanical strength is high, regenerability good for modified silica-gel adsorbent containing two amidoxime group of the present invention; The two amidoxime group groups contained, more effectively can produce chelation with heavy metal, and then better can adsorb the heavy metal ion in waste water, and compared with existing single amidoxime group adsorbent, to Cu
2+absorption property significantly improve, adsorbance brings up to 30mg/g adsorbent.
accompanying drawing illustrates:
Fig. 1 is the flow chart of absorbent preparation of the present invention;
Fig. 2 is reaction unit connection layout: 1 is stirring rod, and 2 is polytetrafluoroethylene (PTFE) plug, and 3 is thermometer, and 4 is thermometer boss, 5
For condenser west tube, 6 is there-necked flask, and 7 is condensed water import, and 8 is condensation-water drain;
Fig. 3 is the graph of a relation that KH550 grafting silica gel and acrylonitrile compolymer reaction temperature affect absorption property;
Fig. 4 is the graph of a relation of adsorbent amount and adsorbance;
Fig. 5 is the kinetic curve figure of adsorbent;
Fig. 6 is the Changing Pattern figure of adsorbent performance with pH value;
Fig. 7 is the adsorption isotherm of adsorbent;
Fig. 8 is the variation diagram of adsorbent performance with multiplexing number.
Detailed description of the invention
Following embodiment further illustrates of the present invention, instead of limit the scope of the invention.
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Composition graphs 1, the preparation method of a kind of modified silica-gel adsorbent containing two amidoxime group that the present invention proposes, comprises the following steps:
Step one, activation: 30g 100-200 object column chromatography silica gel is placed in the pyrovinic acid solution that 150mL volumetric concentration is 5%, condensing reflux at 90 DEG C Keep agitation 4 hours, reacted rear distilled water and repeated to rinse until cleaning solution is in neutral, and at 50 DEG C vacuum drying 24 hours;
Step 2, dipping: the activated silica gel that 10g step one obtains is joined in the toluene solution of 150mL KH550, wherein the volumetric concentration of KH550 is 10%, condensing reflux at 70 DEG C Keep agitation 24 hours, filter to obtain coarse granule, then be that extractant extracts 24 hours in apparatus,Soxhlet's with toluene, remove the unreacted KH550 of Silica Surface, obtain impregnated granules;
Step 3, dry: impregnated granules step 2 obtained vacuum drying 24 hours at 50 DEG C, obtains dried particles;
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide (DMF) solution, wherein the volumetric concentration of acrylonitrile is 15%, then pass into nitrogen, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 65-85 DEG C Keep agitation 5 hours, the modified particles obtained is filtered in reaction afterwards, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, at 70 DEG C of condensing refluxes and Keep agitation 6 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
Embodiment 1:
Step one, activation: 30g 100-200 object column chromatography silica gel is placed in the pyrovinic acid solution that 150mL volumetric concentration is 5%, condensing reflux at 90 DEG C Keep agitation 4 hours, reacted rear distilled water and repeated to rinse until cleaning solution is in neutral, and at 50 DEG C vacuum drying 24 hours;
Step 2, dipping: the activated silica gel that 10g step one obtains is joined in the toluene solution of 150mL KH550, wherein the volumetric concentration of KH550 is 10%, condensing reflux at 70 DEG C Keep agitation 24 hours, filter to obtain coarse granule, then be that extractant extracts 24 hours in apparatus,Soxhlet's with toluene, remove the unreacted KH550 of Silica Surface, obtain impregnated granules;
Step 3, dry: impregnated granules step 2 obtained vacuum drying 24 hours at 50 DEG C, obtains dried particles;
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide (DMF) solution, wherein the volumetric concentration of acrylonitrile is 15%, then pass into nitrogen, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 65 DEG C also continues to stir 5 hours, the modified particles obtained is filtered in reaction afterwards, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, at 70 DEG C of condensing refluxes and Keep agitation 5 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
Embodiment 2:
Step one in repetition embodiment 1 is to three
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide (DMF) solution, wherein the volumetric concentration of acrylonitrile is 15%, then nitrogen is passed into, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 75 DEG C also continues to stir 5 hours, the modified particles obtained is filtered in reaction afterwards, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, at 70 DEG C of condensing refluxes and Keep agitation 5 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
Embodiment 3:
Step one in repetition embodiment 1 is to three
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide (DMF) solution, wherein the volumetric concentration of acrylonitrile is 15%, then nitrogen is passed into, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 85 DEG C also continues to stir 5 hours, the modified particles obtained is filtered in reaction afterwards, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, at 70 DEG C of condensing refluxes and Keep agitation 5 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
Embodiment 4:
Utilize the AO-SiO prepared in embodiment 1-3
2copper ion in adsorbent solution.
(1) AO-SiO of preparation in embodiment 1
2adsorbent
Get the copper ion solution of a series of 50mL variable concentrations, all add the AO-SiO of preparation in 0.075g embodiment 1
2adsorbent, constant temperature oscillation 2h, upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, the concentration of copper ion in mensuration supernatant, according to following formula
obtain adsorbance.Draw the graph of relation of equilibrium concentration and adsorbance, see Fig. 3.
In formula:
for adsorbance (mg/g),
for adsorbing the concentration (mg/L) of copper ion in front solution,
for adsorbing the concentration (mg/L) of copper ion in rear solution,
for liquor capacity (L),
for adsorbent mass (g).
(2) AO-SiO of preparation in embodiment 2
2adsorbent
Get the copper ion solution of a series of 50mL variable concentrations, all add the AO-SiO of preparation in 0.075g embodiment 2
2adsorbent, constant temperature oscillation 2h, upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, the concentration of copper ion in mensuration supernatant, obtains adsorbance.Draw the graph of relation of equilibrium concentration and adsorbance, see Fig. 3.
(3) AO-SiO of preparation in embodiment 3
2adsorbent
Get the copper ion solution of a series of 50mL variable concentrations, all add the AO-SiO of preparation in 0.075g embodiment 3
2adsorbent, constant temperature oscillation 2h, upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, the concentration of copper ion in mensuration supernatant, obtains adsorbance.Draw the graph of relation of equilibrium concentration and adsorbance, see Fig. 3.
When being 75 DEG C as can be seen from accompanying drawing 3, KH550 grafting silica gel and acrylonitrile compolymer temperature, gained adsorbent performance is best.
Embodiment 5:
Utilize the AO-SiO of preparation in embodiment 2
2copper ion in adsorbent solution.
(1) impact of adsorbent amount
Get a series of 50mL concentration be the copper ion solution of 20mg/L in tool plug conical flask, add the adsorbent of different amount respectively, take out solution, and centrifugal with supercentrifuge after, the concentration of copper ion in mensuration supernatant.According to following formula
obtain adsorbance, and draw the relation curve of adsorbance-consumption, see Fig. 4.Can find out the increase along with consumption, adsorbance reduces gradually, but consumption is too small, and eliminating rate of absorption can be caused to decline, and therefore, must select the consumption that moderate, select 1g/L herein.
In formula:
for adsorbance (mg/g),
for adsorbing the concentration (mg/L) of copper ion in front solution,
for adsorbing the concentration (mg/L) of copper ion in rear solution,
for liquor capacity (L),
for adsorbent mass (g).
(2) adsorption dynamics adsorption kinetics
Getting 200mL concentration is that the copper ion solution of 50mg/L is in tool plug conical flask, add 0.15g adsorbent, constant temperature (25 DEG C) vibration in constant temperature oscillator, separated in time taking-up solution also, after using supercentrifuge centrifugal, measures the concentration of copper ion in supernatant.According to following formula
, obtain adsorbance
and draw the relation curve of adsorbance-time, see Fig. 5.As can be seen from the figure, it is shorter that the absorption of adsorbent to copper ion reaches equilibration time, substantially just reaches balance in about 10min absorption.
In formula:
for adsorbance (mg/g),
for adsorbing the concentration (mg/L) of copper ion in front solution,
for the concentration (mg/L) of copper ion in t solution,
for liquor capacity (L),
for adsorbent mass (g).
(3) impact of pH value
Getting a series of 50mL concentration is that the copper ion solution of 20mg/L is in tool plug conical flask, add 0.0375g adsorbent respectively, under condition of different pH, constant temperature oscillation 2h, upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, measure the concentration of copper ion in supernatant, obtain adsorbance, and draw out the relation curve of adsorbance-pH value, see Fig. 6.Can find out that adsorbance increases along with the increase of pH value when pH<6, and actual waste water pH value is faintly acid or neutrality, therefore this is favourable to actual water treatment.
(4) adsorption isotherm model
Get the copper ion solution of a series of 50mL variable concentrations, all add 0.0375g adsorbent, constant temperature oscillation 2h, upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, measure the concentration of copper ion in supernatant, obtain adsorbance, and draw the relation curve of adsorbance-equilibrium concentration, see Fig. 7.Can find out, along with the increase of solution concentration, adsorbance increases gradually, when effects of ion concentration reaches 100mg/L, adsorbance no longer increases along with the increase of concentration, maximal absorptive capacity reaches 30mg/g, and the 9.8mg/g compared in " fiber containing amidoxime groups is to the adsorption dynamics adsorption kinetics of copper (II) " literary composition that the people such as Tao Tingxian deliver in " chemical research and application " improves greatly.
Embodiment 6:
Investigate the recycling performance of made adsorbent.
Utilize embodiment 5(3) in the adsorbent of pH when being 5.5 after absorbing copper ion, with 0.1mol/L watery hydrochloric acid cyclic washing, to remove the copper ion that it adsorbs, be washed with distilled water to cleaning solution neutrality, vacuum drying at 50 DEG C.Get above-mentioned multiplexing adsorbent 0.0375g, joining 50mL concentration is in the copper ion solution of 50mg/L, constant temperature (25 DEG C) vibration in constant temperature oscillator.Repeatedly carry out this series of steps, investigate the change of adsorbance along with multiplexing number.See Fig. 8.Can find out that adsorbance remains unchanged substantially after recycling 5 times, illustrate that regneration of adsorbent material is functional.The invention has the advantages that an amino group can with bimolecular acrylonitrile polymerization, through oximate, form two oximido group, amino a large amount of on it and hydroxyl and heavy metal produce chelation, make adsorption particle have stronger suction-operated to the heavy metal copper ion ratio monoxime base group in solution, adsorption capacity reaches 30mg/g.
Claims (3)
1., containing a modified silica-gel adsorbent for two amidoxime group, it is characterized in that chemical structural formula is:
。
2., containing a preparation method for the modified silica-gel adsorbent of two amidoxime group, it is characterized in that taking silica gel as initiation material, activated → dipping → drying → modification, and the obtained modified silica-gel adsorbent finished product containing two amidoxime group, its concrete steps are as follows:
Step one, activation: 30g 100-200 object column chromatography silica gel is placed in the pyrovinic acid solution that 150mL volumetric concentration is 5%, condensing reflux at 90 DEG C Keep agitation 4 hours, reacted rear distilled water and repeated to rinse until cleaning solution is in neutral, and at 50 DEG C vacuum drying 24 hours;
Step 2, dipping: the activated silica gel that 10g step one obtains is joined in the toluene solution of 150mL KH550, wherein the volumetric concentration of KH550 is 10%, condensing reflux at 70 DEG C Keep agitation 24 hours, filter to obtain coarse granule, then be that extractant extracts 24 hours in apparatus,Soxhlet's with toluene, remove the unreacted KH550 of Silica Surface, obtain impregnated granules;
Step 3, dry: impregnated granules step 2 obtained vacuum drying 24 hours at 50 DEG C, obtains dried particles;
Step 4, modification:
(1) dried particles that 5g step 3 obtains is joined the N of 100mL acrylonitrile, in dinethylformamide solution, wherein the volumetric concentration of acrylonitrile is 15%, then nitrogen is passed into, get rid of the air in bottle, add 0.1g initator azodiisobutyronitrile again, condensing reflux at 65-85 DEG C Keep agitation 5 hours, filter after reaction and obtain a modified particles, with N, dinethylformamide is that extractant extracts 24 hours in apparatus,Soxhlet's, remove the unreacted acrylonitrile of Silica Surface, obtain dipping modified particles, and at 50 DEG C vacuum drying 24 hours, obtain oven dry modified particles,
(2) sodium carbonate liquor be hydroxylamine hydrochloride solution and the 20mL concentration of 1mol/L by 20mL concentration being 1mol/L mixes, after add the oven dry modified particles obtained in 1g step 4 (1), then nitrogen is passed into, remove the air in bottle, condensing reflux at 70 DEG C Keep agitation 6 hours, filter after reaction and obtain twice-modified particle, it is neutral for purifying to cleaning solution with distilled water cyclic washing again, be purified twice-modified particle, and at 50 DEG C vacuum drying 24 hours, obtain drying twice-modified particle, be the modified silica-gel adsorbent finished product containing two amidoxime group.
3. the preparation method of the modified silica-gel adsorbent containing two amidoxime group according to claim 2, is characterized in that the reaction temperature in step 4 (1) is 75 DEG C.
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| CN103752279A (en) * | 2013-11-27 | 2014-04-30 | 河海大学 | Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof |
| TWI671312B (en) | 2014-01-17 | 2019-09-11 | 美商健臻公司 | Sterile chromatography and manufacturing processes |
| TWI709569B (en) | 2014-01-17 | 2020-11-11 | 美商健臻公司 | Sterile chromatography resin and use thereof in manufacturing processes |
| CN105936824B (en) * | 2016-04-06 | 2021-04-06 | 深圳多元拓展环保科技有限公司 | Soil heavy metal activator and preparation method and application thereof |
| CN108359610B (en) * | 2018-02-06 | 2021-10-15 | 南华大学 | Bisaminidoxime-modified facultative marine fungus repairing agent and method for repairing uranium-polluted water body |
| CN108404870B (en) * | 2018-04-20 | 2021-05-04 | 中国科学院合肥物质科学研究院 | Microporous carboxylated silica gel, preparation method and application thereof |
| CN108654558A (en) * | 2018-04-26 | 2018-10-16 | 武汉理工大学 | A kind of X-type zeolite and preparation method thereof being modified together with amidoxime, to the adsorption applications of ruthenium and caesium |
| CN112638488A (en) | 2018-08-31 | 2021-04-09 | 建新公司 | Sterilized chromatography resin and use thereof in manufacturing process |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (1)
| Title |
|---|
| 基于复合型螯合材料PAO/SiO2的重金属离子吸附与稀土离子表面印迹的研究;高学超;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20110515(第5期);第11-21页 * |
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