CN107899553A - A kind of adsorbent containing imidazoline structure and preparation method thereof - Google Patents
A kind of adsorbent containing imidazoline structure and preparation method thereof Download PDFInfo
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- CN107899553A CN107899553A CN201711211100.9A CN201711211100A CN107899553A CN 107899553 A CN107899553 A CN 107899553A CN 201711211100 A CN201711211100 A CN 201711211100A CN 107899553 A CN107899553 A CN 107899553A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- B01J2220/00—Aspects relating to sorbent materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of adsorbent containing imidazoline structure and preparation method thereof, belongs to environmentally friendly water process, heavy metal removal technology field.The present invention is using 1 (2 N pi-allyls aminoethyl) 2 oily acid based imidazolines, acrylamide and acrylonitrile as Material synthesis ter-polymers, and then with chitosan crosslinked, then the oximate through hydroxylamine hydrochloride obtains the adsorbent A m PN CTS containing imidazoline structure.The adsorbent containing imidazoline structure prepared by the present invention is strong to heavy metal ion adsorbed ability, removal efficiency is high.
Description
Technical field
The present invention relates to environmentally friendly water process, heavy metal removal technology field, and in particular to a kind of sorbing material, more particularly to
A kind of adsorbent containing imidazoline structure and preparation method thereof.
Background technology
With the continuous development of process of industrialization, the pollution problem of water resource becomes increasingly conspicuous, especially containing heavy metal ion
Industrial wastewater.Although heavy metal is trace element necessary to the mankind, but the mankind are minimum to its tolerance, only in vivo
Accumulation reaches small amount will cause greatly to damage to function of human body, likewise, can also bring serious existence prestige to animals and plants
The side of body.Therefore, domestic and foreign scholars investigated the processing method pollution administration problem such as chemical precipitation method, ion-exchange, absorption method,
Research achieves certain achievement, but in the rate of adsorption, adsorbance, energy consumption and using still suffering from defect in portability.
The content of the invention
It is an object of the invention to provide a kind of adsorbent containing imidazoline structure and preparation method thereof, to solve existing suction
The problem of enclosure material adsorption effect is bad.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of adsorbent containing imidazoline structure, its general structure are：
Wherein, n, the mole percent that x, y, z is construction unit, n=9.99~30.73%, x=59.76~
77.66%, y=8.90~11.56%, z=0.61~0.79%.
The preparation method of the above-mentioned adsorbent containing imidazoline structure, including：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1
Mass ratio add into deionized water and stir under an inert atmosphere, add the Asia for accounting for three kinds of monomer gross mass 0.2%
Niter cake-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then,
Flow back 6h at 45 DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made；
(2) chitosan CTS is dissolved in aqueous acetic acid, then according to PN 49.5~79.2%, CTS19.8~
49.5%th, the mass percent of glutaraldehyde cross-linking agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, is made
Compound PN-CTS；
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
Further, in preferred embodiments of the present invention, step (2) further includes：Purification, drying and pulverising step.
Further, in preferred embodiments of the present invention, in step (2), purified with absolute ethyl alcohol.
Further, in preferred embodiments of the present invention, step (3) includes step in detail below：
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：The ratio of (1~1.3) takes chemical combination
Thing PN-CTS and hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction that quality of oxammonium hydrochloride fraction is 3%
Liquid, wherein, the volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, after
Continuous reaction 2h, is made the adsorbent containing imidazoline structure.
Further, in preferred embodiments of the present invention, in step (32), the NaOH solution for being 1mol/L with concentration
Adjust pH value.
Further, in preferred embodiments of the present invention, step (32) further includes：After the completion of reaction, filtered,
Filtrate is cleaned with ethanol, then vacuum drying.
The invention has the advantages that：
The present invention provides a kind of adsorbent containing imidazoline structure, with 1- (2-N- pi-allyls aminoethyl) -2- oleic acid bases
Imidazoline, acrylamide and acrylonitrile are Material synthesis ter-polymers：Poly- (1- (2-N- pi-allyls aminoethyl) -2- oleic acid bases
Imidazoline/acrylamide/acrylonitrile) PN, and then by PN with chitosan crosslinked, then the oximate through hydroxylamine hydrochloride obtains containing imidazoline
The adsorbent A m-PN-CTS of structure.
The present invention introduces imidazolinyl and the difunctional adsorption site of amidoxime group in sorbent structure, can quickly lead to
Cross absorption of the chelation realization to heavy metal；Due to chitosan no biotoxicity itself, have good mechanical strength and into
Film and good bactericidal effect, are Green Water Treatment Reagents, and therefore, the present invention lifts further suction by cross-linked chitosan
Attached dose of performance.
Meanwhile this chitosan crosslinked sorbent structure containing imidazoline and amidoxim dual-functional group of the invention, use
Biodegradable, no biotoxicity, the natural polymer raw materials of chitosan derived from a wealth of sources, with reference to imidazoline group and amidoxim
The specific physicochemical property that group dual functional polymer is assigned removes the heavy metal in waste water so that adsorbent of the invention has
The advantages that regenerability is good, and adsorption rate is fast, has broad application prospects in terms of Adsorption heavy metal.
It should be noted that for the ease of description, the present invention with abridge " PN " replace product made from above-mentioned steps (1)：
Poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile).PN-CTS refers to by poly- (1- (2-
N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) and chitosan generation compound.Am-PN-CTS
Refer to the compound PN-CTS after oximate is handled, " Am " is not necessarily referring to some reaction monomers, but represents the meaning of oximate processing
Think.
Brief description of the drawings
Fig. 1 is the reacting flow chart of the adsorbent of the invention containing imidazoline structure；
Fig. 2 is poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) of the invention (contracting
Write PN) infrared spectrum；
Fig. 3 is the infrared spectrum of the adsorbent of the invention containing imidazoline structure；
Fig. 4 is the SEM image of the adsorbent of the invention containing imidazoline structure；
Fig. 5 is the adsorbent of the invention containing imidazoline structure to various heavy absorption property design sketch.
Embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.The person that is not specified actual conditions in embodiment, the bar suggested according to normal condition or manufacturer
Part carries out.Reagents or instruments used without specified manufacturer, is the conventional products that can be obtained by commercially available purchase.
The adsorbent containing imidazoline structure of the present invention, its general structure are：
Wherein, n, mole percent n=9.99~30.73% that x, y, z is construction unit, x=59.76~77.66%,
Y=8.90~11.56%, z=0.61~0.79%.
Adsorbent containing imidazoline structure, its chemical name are：Poly- (1- (2-N- pi-allyls the aminoethyl) -2- of amidoximization
Oily acid based imidazolines/acrylamide/acrylonitrile) grafted chitosan.Fig. 1 is the adsorbent containing imidazoline structure for preparing the present invention
Reacting flow chart.The present invention will advance obtained poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acryloyl
Amine/acrylonitrile) (being abbreviated as PN) and chitosan (being abbreviated as CTS) reaction, compound PN-CTS is generated, then to compound
PN-CTS carries out oximate processing, generates compound Am-PN-CTS, i.e. adsorbent of the end-product containing imidazoline structure.
The reaction of the embodiment of the present invention carries out in three-neck flask.
Embodiment 1
The preparation method of the adsorbent containing imidazoline structure of the present embodiment comprises the following steps：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1
Mass ratio add into deionized water and stir under an inert atmosphere, add the Asia for accounting for three kinds of monomer gross mass 0.2%
Niter cake-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then,
Flow back 6h at 45 DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made.
The inert atmosphere that this step is related to can be nitrogen, argon gas or helium.
(2) chitosan CTS is dissolved in aqueous acetic acid, is then handed over according to PN 79.2%, CTS 19.8%, glutaraldehyde
The mass percent for joining agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, compound PN-CTS is made.
Purification, drying and pulverising step.Purified with absolute ethyl alcohol.
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：1 ratio takes compound PN-CTS
And hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction solution that quality of oxammonium hydrochloride fraction is 3%, wherein,
The volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, after
Continuous reaction 2h, is made the adsorbent containing imidazoline structure.After the completion of reaction, filtered, filtrate ethanol is clear
Wash, then vacuum drying.
Embodiment 2
The preparation method of the adsorbent containing imidazoline structure of the present embodiment comprises the following steps：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1
Mass ratio add into deionized water and stir under an inert atmosphere, add the Asia for accounting for three kinds of monomer gross mass 0.2%
Niter cake-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then,
Flow back 6h at 45 DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made.
The inert atmosphere that this step is related to can be nitrogen, argon gas or helium.
(2) chitosan CTS is dissolved in aqueous acetic acid, is then handed over according to PN 69.3%, CTS 29.7%, glutaraldehyde
The mass percent for joining agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, compound PN-CTS is made.
Purification, drying and pulverising step.Purified with absolute ethyl alcohol.
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：1.2 ratio takes compound PN-
CTS and hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction solution that quality of oxammonium hydrochloride fraction is 3%, its
In, the volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, after
Continuous reaction 2h, is made the adsorbent containing imidazoline structure.After the completion of reaction, filtered, filtrate ethanol is clear
Wash, then vacuum drying.
Embodiment 3
The preparation method of the adsorbent containing imidazoline structure of the present embodiment comprises the following steps：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1
Mass ratio add into deionized water and stir under an inert atmosphere, add the Asia for accounting for three kinds of monomer gross mass 0.2%
Niter cake-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then,
Flow back 6h at 45 DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made.
The inert atmosphere that this step is related to can be nitrogen, argon gas or helium.
(2) chitosan CTS is dissolved in aqueous acetic acid, is then handed over according to PN 59.4%, CTS 39.6%, glutaraldehyde
The mass percent for joining agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, compound PN-CTS is made.
Purification, drying and pulverising step.Purified with absolute ethyl alcohol.
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：1.3 ratio takes compound PN-
CTS and hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction solution that quality of oxammonium hydrochloride fraction is 3%, its
In, the volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, after
Continuous reaction 2h, is made the adsorbent containing imidazoline structure.After the completion of reaction, filtered, filtrate ethanol is clear
Wash, then vacuum drying.
Embodiment 4
The preparation method of the adsorbent containing imidazoline structure of the present embodiment comprises the following steps：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1
Mass ratio add into deionized water and stir under an inert atmosphere, add the Asia for accounting for three kinds of monomer gross mass 0.2%
Niter cake-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then,
Flow back 6h at 45 DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made.
The inert atmosphere that this step is related to can be nitrogen, argon gas or helium.
(2) chitosan CTS is dissolved in aqueous acetic acid, is then handed over according to PN 49.5%, CTS 49.5%, glutaraldehyde
The mass percent for joining agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, compound PN-CTS is made.
Purification, drying and pulverising step.Purified with absolute ethyl alcohol.
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：1.15 ratio takes compound PN-
CTS and hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction solution that quality of oxammonium hydrochloride fraction is 3%, its
In, the volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, after
Continuous reaction 2h, is made the adsorbent containing imidazoline structure.After the completion of reaction, filtered, filtrate ethanol is clear
Wash, then vacuum drying.
Adsorbent produced by the present invention containing imidazoline structure is canescence puffy thing.
The structural characterization of test example 1PN
To (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/the third poly- made from above-described embodiment
Alkene nitrile) PN characterized.Since the collection of illustrative plates that embodiment 1-4 is obtained is essentially identical, PN is made with embodiment 1 and carries out caption.
Structural analysis is carried out by infrared spectrum to sample prepared by embodiment 1, using KBr pressed disc methods, passes through WQF-
510A Fourier transformation infrared spectrometers are to poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/the third
Alkene nitrile) (PN) structure characterized, and infrared spectrum is as shown in Figure 2.It is the analysis to principal character peak and ownership below：
From figure 2 it can be seen that 3356cm-1Strong list absworption peak is the stretching vibration ν of the N-H keys of acid amides in placeNH；C h bond
Asymmetric and symmetrical stretching vibration frequency is respectively in 2934cm-1And 2865cm-1Place, 1448cm-1Locate as-CH2- flexural vibrations
Peak, 1350cm-1Locate to absorb for secondary amine C-N stretching vibrations, 2249cm-1The spike at place is the stretching vibration absworption peak of C ≡ N.
Thus sample structure and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/the third are inferred
Alkene nitrile) (PN) structure is consistent.
The structural characterization of adsorbent of the test example 2 containing imidazoline structure
Equally illustrated with embodiment 1 for representative.
Structural analysis is carried out by infrared spectrum to sample prepared by embodiment 1, using KBr pressed disc methods, passes through WQF-
510A Fourier transformation infrared spectrometers characterize the adsorbent A m-PN-CTS containing imidazoline structure, as shown in Figure 3.With
Under be analysis and ownership to principal character peak：
3670-3076cm-1Nearby strong and wide absorption band is OH stretching vibration frequencies νOHWith the N-H stretching vibrations of acid amides
Frequency νNH, 2935cm-1The C-H stretching vibration peaks at place slightly strengthen, 2249cm-1Neighbouring C ≡ N key stretching vibration absworption peaks disappear
Lose, it was demonstrated that there occurs amidoximation.
Thus infer that the synthesized adsorbent A m-PN-CTS containing imidazoline structure is consistent with expection, i.e., successfully synthesize
Adsorbent containing imidazoline structure.
The Microstructure characterization of adsorbent of the test example 3 containing imidazoline structure
Equally illustrated with embodiment 1 for representative.
Using 450 scanning electron microscope of FEI Quanta (U.S., FEI Co.) to the adsorbent containing imidazoline structure,
That is Am-PN-CTS carries out microscopic pattern scanning, obtains its SEM image.Sample is fully dry, then sticked at conducting resinl
On silicon chip, metal spraying, is then transferred to the scanning electron microscopy with cryogenic sample platform, changes and the microcosmic of material is scanned under voltage conditions
Structure.
It can be observed from Fig. 4, the adsorbent surface containing imidazoline structure is very loose, and the sky of abundance is provided for adsorbate
Between interact.Adsorbent containing imidazoline structure, i.e. Am-PN-CTS, the uniform gap structure having, make it compare table
Area increase, helps to contact with adsorbate, improves its adsorption capacity.
Removal of adsorbent of the test example 4 containing imidazoline structure to various heavy in solution
Equally illustrated with embodiment 1 for representative.
Take adsorbent prepared by 0.1g embodiments 1 to be placed in 100mL heavy metal water samples, contain in untreated heavy metal water sample
Cu2+、Pb2+、Ni2+、Cr2+Mass concentration is respectively 50.28mg/L, 19.65mg/L, 12.11mg/L, 7.83mg/L, is stood
500s, solution concentration after being handled with Inductively coupled plasma optical emission spectrometer measure, and calculate removal rate.Solution after final process
Middle Cu2+、Pb2+、Ni2+、Cr2+Mass concentration is respectively 0.43,0.91,0.47,0.86mg/L, before and after removal GOLD FROM PLATING SOLUTION category from
As a result the concentration of son meets as shown in figure 5, removal rate is respectively 99.14%, 95.37%, 96.12%, 89.02%《Sewage is comprehensive
Close discharge standard》.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of adsorbent containing imidazoline structure, it is characterised in that its general structure is：
Wherein, n, the mole percent that x, y, z is construction unit, n=9.99~30.73%, x=59.76~77.66%, y=
8.90~11.56%, z=0.61~0.79%.
2. the preparation method of the adsorbent containing imidazoline structure described in claim 1, it is characterised in that including：
(1) 1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines, acrylamide and acrylonitrile is taken according to 0.5:9:1 matter
Amount ratio is added into deionized water and stirred under an inert atmosphere, adds the sulfurous acid for accounting for three kinds of monomer gross mass 0.2%
Hydrogen sodium-ammonium persulfate redox initiator, wherein, the molar ratio of sodium hydrogensulfite and ammonium persulfate is 1:1；Then, 45
Flow back 6h at DEG C, and poly- (1- (2-N- pi-allyls aminoethyl) -2- oil acid based imidazolines/acrylamide/acrylonitrile) PN is made；
(2) chitosan CTS is dissolved in aqueous acetic acid, then according to PN 49.5~79.2%, CTS 19.8~49.5%,
The mass percent of glutaraldehyde cross-linking agent 1.0% adds, and is stirred evenly at 55 DEG C, after complete reaction, compound is made
PN-CTS；
(3) compound PN-CTS is subjected to oximate processing, the adsorbent containing imidazoline structure is made.
3. the preparation method of the adsorbent according to claim 2 containing imidazoline structure, it is characterised in that step (2) is also
Including：Purification, drying and pulverising step.
4. the preparation method of the adsorbent according to claim 3 containing imidazoline structure, it is characterised in that in step (2)
In, purified with absolute ethyl alcohol.
5. the preparation method of the adsorbent according to claim 2 containing imidazoline structure, it is characterised in that step (3) is wrapped
Include step in detail below：
(31) it is 1 according to the molar ratio of cyano group and hydroxylamine hydrochloride in compound PN-CTS：The ratio of (1~1.3) takes compound PN-
CT and hydroxylamine hydrochloride, the mixed solvent formed with first alcohol and water are configured to the reaction solution that quality of oxammonium hydrochloride fraction is 3%, its
In, the volume ratio of the in the mixed solvent methanol and water is 1:1；
(32) reaction solution made from step (31) is flowed back 2h in inert atmosphere at 85 DEG C, then adjusts pH to 7, continued anti-
2h is answered, the adsorbent containing imidazoline structure is made.
6. the preparation method of the adsorbent according to claim 5 containing imidazoline structure, it is characterised in that in step (32)
In, the NaOH solution for being 1mol/L with concentration adjusts pH value.
7. the preparation method of the adsorbent according to claim 5 containing imidazoline structure, it is characterised in that step (32) is also
Including：After the completion of reaction, filtered, filtrate is cleaned with ethanol, then vacuum drying.
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| CN110523396A (en) * | 2019-09-10 | 2019-12-03 | 兰州大学 | A kind of uranium separation method and uranium absorption material |
| CN111454723A (en) * | 2020-04-09 | 2020-07-28 | 上海园林（集团）有限公司 | Soil treatment solution for treating heavy metals in polluted soil in ecological gardens |
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| CN104710566A (en) * | 2015-03-19 | 2015-06-17 | 西南石油大学 | Terpolymer oil-displacing agent containing imidazoline structure and preparation of terpolymer oil-displacing agent |
| CN106311164A (en) * | 2016-11-04 | 2017-01-11 | 西南石油大学 | Amidoxime group-containing chitosan modified adsorbent and preparation method thereof |
| CN106902747A (en) * | 2017-03-29 | 2017-06-30 | 东华理工大学 | A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof |
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| CN103816872A (en) * | 2013-11-04 | 2014-05-28 | 南华大学 | Magnetic hydroxamic chitosan and preparation method thereof |
| CN104152130A (en) * | 2014-07-03 | 2014-11-19 | 西南石油大学 | AM /NaAA/NIDA hydrophobic association polymer oil displacement agent and synthetic method thereof |
| CN104710566A (en) * | 2015-03-19 | 2015-06-17 | 西南石油大学 | Terpolymer oil-displacing agent containing imidazoline structure and preparation of terpolymer oil-displacing agent |
| CN106311164A (en) * | 2016-11-04 | 2017-01-11 | 西南石油大学 | Amidoxime group-containing chitosan modified adsorbent and preparation method thereof |
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| CN110523396A (en) * | 2019-09-10 | 2019-12-03 | 兰州大学 | A kind of uranium separation method and uranium absorption material |
| CN111454723A (en) * | 2020-04-09 | 2020-07-28 | 上海园林（集团）有限公司 | Soil treatment solution for treating heavy metals in polluted soil in ecological gardens |
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