CN109776744A - A kind of preparation method of amidoxime-silica resin for adsorbing gallium - Google Patents
A kind of preparation method of amidoxime-silica resin for adsorbing gallium Download PDFInfo
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- CN109776744A CN109776744A CN201910028890.XA CN201910028890A CN109776744A CN 109776744 A CN109776744 A CN 109776744A CN 201910028890 A CN201910028890 A CN 201910028890A CN 109776744 A CN109776744 A CN 109776744A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 62
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 acrylonitrile-dicarbonate Chemical compound 0.000 claims abstract description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000008188 pellet Substances 0.000 claims abstract description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 3
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims description 27
- 229910052682 stishovite Inorganic materials 0.000 claims description 27
- 229910052905 tridymite Inorganic materials 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 20
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 11
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000009434 installation Methods 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical group C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicon Compounds (AREA)
Abstract
本发明公开了一种吸附镓的偕胺肟‑二氧化硅树脂的制备方法，以一种介孔二氧化硅微球作为骨架，以丙烯腈为主要原料，利用溶液聚合法合成丙烯腈‑二氧化硅小球（PAN/SiO2树脂），并通过胺肟化反应嫁接偕胺肟功能基团，对丙烯腈‑二氧化硅小球进行改性，从而得到偕胺肟‑二氧化硅树脂(PAO/SiO2)。该树脂吸附剂具有发达的有序介孔结构、大比表面积、良好的机械强度和化学稳定性，便于镓快速进入孔道内吸附，适用于拜耳溶液中镓的分离回收，反应过程中无需加入任何化学试剂，无污染且不产生任何废弃物。该树脂对镓的吸附容量较高、选择性好、吸附速度快等特性，具有广阔的市场前景。
The invention discloses a preparation method of amidoxime-silica resin for adsorbing gallium. A mesoporous silica microsphere is used as a skeleton, acrylonitrile is used as a main raw material, and acrylonitrile-dicarbonate is synthesized by a solution polymerization method. Silica pellets (PAN/SiO 2 resin), and grafting amidoxime functional groups through amidoximation reaction, and modifying acrylonitrile-silica pellets to obtain amidoxime-silica resin ( PAO/SiO 2 ). The resin adsorbent has a well-developed ordered mesoporous structure, large specific surface area, good mechanical strength and chemical stability, which facilitates the rapid entry of gallium into the pores for adsorption, and is suitable for the separation and recovery of gallium in Bayer solution. Chemical reagents, no pollution and no waste. The resin has the characteristics of high adsorption capacity, good selectivity and fast adsorption speed for gallium, and has broad market prospects.
Description
Technical field
The invention belongs to technical field of resource recovery, specifically, being related to a kind of amidoxim-silica tree for adsorbing gallium
The preparation method of rouge.
Background technique
Gallium is the important support material of contemporary new and high technology, is mainly used for electronics as the important member in dissipated metal
The fields such as industry, chemical industry, new energy, instrumentation industry and medicine.Wherein, semicon industry has become the maximum consumption neck of gallium
Domain accounts for about the 80% of aggregate consumption.
Currently, 90% former gallium recycles in the bayer liquor in aluminum oxide production process.Gallium is extracted from bayer liquor
The main method for using ion exchange, however, commercial ion exchange resin, partial size is very big, and specific surface area is small, the time of absorption
Long, expansion rate is big, is easy to happen fragmentation during absorption.
Summary of the invention
In view of this, the present invention provides a kind of amidoxim-silica resin preparation methods for adsorbing gallium.
In order to solve the above-mentioned technical problem, the invention discloses a kind of amidoxim-silica resin systems for adsorbing gallium
Preparation Method, comprising the following steps:
Step 1 prepares acrylonitrile-silica resin (PAN/SiO2): using mesoporous silicon dioxide micro-sphere as skeleton, with
Acrylonitrile is raw material, utilizes solution polymerization process synthesis of acrylonitrile-silica resin (PAN/SiO2)；
Amidoxim-silica resin (PAO/SiO of step 2, preparation absorption gallium2): by amidoximation grafting together with
Amidoxime functional group is modified acrylonitrile-silicon oxide pellets, obtains amidoxim-silica resin of absorption gallium
(PAO/SiO2)。
Optionally, acrylonitrile-silica resin (PAN/SiO is prepared in the step 12) its synthetic route such as
Under:
The following steps are included: selection silica dioxide granule makees skeleton；Silica dioxide granule is put into rotary evaporation flask
And it is extracted into negative pressure using vacuum pump, nitrogen cylinder is then connected, nitrogen is introduced, vacuumizes；Then by monomer, diluent and initiator
Mixture suck-back enter in flask；The rotation speed for adjusting Rotary Evaporators keeps mixture and silica dioxide granule sufficiently mixed
It closes；Hereafter, it is heated in silicone oil bath；Obtained silica grafted propylene nitrile resin is cleaned respectively with acetone and water to remove
The polymer of physical attachment, is dried under vacuum, and finally obtains grafted particles PAN/SiO2。
Optionally, the partial size of the silica dioxide granule is 70-150 μm；Pumpdown time is 25-35 minutes.
Optionally, monomer: diluent: the mass ratio of initiator is 90-110:320-380:0.5-1.5.
Optionally, the monomer is the divinylbenzene and acrylonitrile that mass ratio is 20:80-10:90；Diluent is matter
Amount is than the acetophenone and diethyl phthalate for 3:2；Initiator is azodiisobutyronitrile.
Optionally, it is heated in silicone oil bath specifically: be slowly heated to 343K, keep 0.5h-1.5h, then add at 353K
Hot 1.5h-2.5h, it is finally heated to 363K holding 6.5h-7.5h.
Optionally, amidoxim-silica resin synthetic route of preparation absorption gallium is as follows in the step 2:
The following steps are included: removing ionized water and ethyl alcohol mixing；In a nitrogen atmosphere, by hydroxylamine hydrochloride, it is mixed to be dissolved in this
It closes in solution, the sodium carbonate being then added under magnetic stirring at room temperature, on the other hand, by PAN/SiO2Resin and mixing are molten
Liquid is added in three-neck flask, then system is heated to 343K, and under nitrogen atmosphere in a water bath by installation condensation return mechanism
Heating；It is filtered, after washing and drying, finally obtains the PAO/SiO of synthesis2Resin.
Optionally, the deionized water and the volume ratio of ethyl alcohol are 1:1；The quality volume of hydroxylamine hydrochloride and deionized water
It is 5:100-10:100 than (g/ml), the mass volume ratio (g/ml) of sodium carbonate and deionized water is 3:100-5:100.
Optionally, the PAN/SiO2Resin and the mass volume ratio (g/ml) of deionized water are 8:100-12:100；
The time of water-bath is 2.5h-3.5h.
Compared with prior art, the present invention can be obtained including following technical effect:
1) resin sorbent has flourishing ordered mesopore structure, bigger serface, good mechanical strength and chemistry
Stability, the separation and recovery of gallium suitable for bayer liquor is pollution-free and not without being added any chemical reagents in reaction process
Generate any waste.
2) resin is higher to the adsorption capacity of gallium, adsorption rate is fast, selectivity is preferable, has a vast market foreground.
Certainly, it implements any of the products of the present invention it is not absolutely required to while reaching all the above technical effect.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is PAO/SiO of the present invention2Synthetic schemes.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below in conjunction with embodiment, whereby to the present invention how application technology hand
Section solves technical problem and reaches the realization process of technical effect to fully understand and implement.
The invention discloses a kind of amidoxim-silica resin preparation methods for adsorbing gallium, comprising the following steps:
Step 1, PAN/SiO2The preparation of resin, synthetic route are as follows:
The following steps are included: selecting 70-150 μm of silica dioxide granule as the skeleton of fluoropolymer resin.By titanium dioxide
Silicon particle is put into rotary evaporation flask and is extracted into negative pressure using vacuum pump, then connects nitrogen cylinder, introduces nitrogen, vacuumizes
25-35 minutes.Then by monomer, the mixture suck-back of diluent and initiator enters in flask, wherein monomer: diluent: draws
The mass ratio for sending out agent is 90-110:320-380:0.4-1.5；Monomer is the divinylbenzene that mass ratio is 20:80-10:90
(DVB) and acrylonitrile；Diluent is the acetophenone and diethyl phthalate that mass ratio is 3:2；Initiator is that azo two is different
Butyronitrile；The rotation speed for adjusting Rotary Evaporators, is sufficiently mixed mixture with silica dioxide granule.Hereafter, in silicone oil bath
It is slowly heated to 343K, keeps 0.5h-1.5h, 1.5h-2.5h is then heated at 353K, it is finally heated to 363K holding
6.5h-7.5h.Obtained silica grafted propylene nitrile resin is cleaned with acetone and water respectively to remove the poly- of physical attachment
Object is closed, is dried under vacuum, grafted particles PAN/SiO is finally obtained2。
Step 2, PAO/SiO2The preparation of resin, synthetic route are as follows:
The following steps are included: removing ionized water and ethyl alcohol according to volume ratio is 1:1 mixing；In a nitrogen atmosphere, by hydrochloric acid
Azanol is dissolved in the mixed solution, wherein hydroxylamine hydrochloride and the mass volume ratio (g/ml) of deionized water are 5:100-10:
100, the sodium carbonate being then added under magnetic stirring at room temperature, wherein the mass volume ratio (g/ of sodium carbonate and deionized water
It ml) is 3:100-5:100；On the other hand, by PAN/SiO2Resin and mixed solution are added in three-neck flask, wherein PAN/
SiO2Resin and the mass volume ratio (g/ml) of deionized water are 8:100-12:100；Installation condenses return mechanism, then will be
System is heated to 343K, and keeps 2.5h-3.5h in a water bath under nitrogen atmosphere；It is filtered, after washing and drying, finally obtains conjunction
At PAO/SiO2Resin.
1 degree of cross linking of embodiment is 8%, the PAO/SiO that organic content is 20%2Preparation
Silica dioxide granule is put into rotary evaporation flask and is extracted into negative pressure using vacuum pump, then connects nitrogen cylinder,
Nitrogen is introduced, is vacuumized 30 minutes.Then by monomer 25g (DVB and acrylonitrile that mass ratio is 15:85), diluent 350g (matter
Amount than be 3:2 acetophenone and diethyl phthalate) and initiator 1g (azodiisobutyronitrile) mixture suck-back entrance
In flask.The rotation speed for adjusting Rotary Evaporators, is sufficiently mixed mixture with silica dioxide granule.Hereafter, in silicone oil bath
In be slowly heated to 343K, kept for 1 hour, then heat 2 hours at 353K, it is finally heated to 363K holding 7 hours.Will
To silica grafted propylene nitrile resin cleaned with acetone and water to remove the polymer of physical attachment respectively, do under vacuum
It is dry, finally obtain grafted particles PAN/SiO2.Then carry out amidoxim function dough arrives PAO/SiO2Resin.
The organic content of resulting resin thermogravimetric analysis is 15%, surface area 283m2/ g, pore volume 0.73cm3/ g,
Hole size isThe C:N:O of elemental analysis is respectively 10.98:1.57:3.75, and the static adsorbance to gallium is 3.23mg/g.
2 degree of cross linking of embodiment is 15%, the PAO/SiO that organic content is 25%2Preparation
Silica dioxide granule is put into rotary evaporation flask and is extracted into negative pressure using vacuum pump, then connects nitrogen cylinder,
Nitrogen is introduced, is vacuumized 30 minutes.Then by monomer 33g (DVB and acrylonitrile that mass ratio is 10:90), 117g diluent (matter
Amount than be 3:2 acetophenone and diethyl phthalate) and initiator 0.4g (azodiisobutyronitrile) mixture suck-back into
Enter in flask.The rotation speed for adjusting Rotary Evaporators, is sufficiently mixed mixture with silica dioxide granule.Hereafter, in silicone oil
It is slowly heated to 343K in bath, is kept for 1 hour, is then heated 2 hours at 353K, it is finally heated to 363K holding 7 hours.It will
Obtained silica grafted propylene nitrile resin is cleaned with acetone and water to remove the polymer of physical attachment, under vacuum respectively
It is dry, finally obtain grafted particles PAN/SiO2.Then carry out amidoxim function dough arrives PAO/SiO2Resin.
The organic content of resulting resin thermogravimetric analysis is 20.43%, surface area 303m2/ g, pore volume 0.69cm3/
G, hole size areThe C:N:O of elemental analysis is respectively 12.55:1.64:4.04, and the static adsorbance to gallium is
4.40mg/g。
Embodiment 3
Select 70 μm of silica dioxide granule as the skeleton of fluoropolymer resin.Silica dioxide granule is put into rotary evaporation
It is extracted into negative pressure in flask and using vacuum pump, then connects nitrogen cylinder, nitrogen is introduced, vacuumizes 25 minutes.Then by monomer 90g
(DVB and acrylonitrile that mass ratio is 20:80), (mass ratio is the acetophenone and phthalic acid diethyl of 3:2 to 380g diluent
Ester) and the mixture suck-back of 0.4g initiator (azodiisobutyronitrile) enter in flask, adjust the rotation speed of Rotary Evaporators,
It is sufficiently mixed mixture with silica dioxide granule.Hereafter, it is slowly heated to 343K in silicone oil bath, keeps 0.5h, then exists
2.5h is heated under 353K, it is finally heated to 363K holding 6.5h.Obtained silica grafted propylene nitrile resin is used third respectively
Ketone and water are cleaned to remove the polymer of physical attachment, are dried under vacuum, and grafted particles PAN/SiO is finally obtained2。
It is 1:1 mixing that ionized water and ethyl alcohol, which are removed, according to volume ratio；In a nitrogen atmosphere, by hydroxylamine hydrochloride, it is dissolved in this
In mixed solution, wherein hydroxylamine hydrochloride and the mass volume ratio (g/ml) of deionized water are 5:100, then at room temperature in magnetic
The sodium carbonate that power is added with stirring, wherein sodium carbonate and the mass volume ratio (g/ml) of deionized water are 5:100；On the other hand,
By PAN/SiO2Resin and mixed solution are added in three-neck flask, wherein PAN/SiO2The quality volume of resin and deionized water
It is 8:100 than (g/ml)；Installation condensation return mechanism, is then heated to 343K for system, and protect in a water bath under nitrogen atmosphere
Hold 3.5h；It is filtered, after washing and drying, finally obtains the PAO/SiO of synthesis2Resin.
Embodiment 4
Select 150 μm of silica dioxide granule as the skeleton of fluoropolymer resin.Silica dioxide granule is put into rotation to steam
It is extracted into negative pressure in fever bottle and using vacuum pump, then connects nitrogen cylinder, nitrogen is introduced, vacuumizes 35 minutes.Then by monomer
(mass ratio is the acetophenone and phthalic acid two of 3:2 by 110g (DVB and acrylonitrile that mass ratio is 15:85), diluent 320g
Ethyl ester) and the mixture suck-back of initiator 1.5g (azodiisobutyronitrile) enter in flask；Adjust the rotation speed of Rotary Evaporators
Degree, is sufficiently mixed mixture with silica dioxide granule.Hereafter, it is slowly heated to 343K in silicone oil bath, keeps 1.5h, then
1.5h is heated at 353K, it is finally heated to 363K holding 7.5h.Obtained silica grafted propylene nitrile resin is used respectively
Acetone and water are cleaned to remove the polymer of physical attachment, are dried under vacuum, and grafted particles PAN/SiO is finally obtained2。
It is 1:1 mixing that ionized water and ethyl alcohol, which are removed, according to volume ratio；In a nitrogen atmosphere, by hydroxylamine hydrochloride, it is dissolved in this
In mixed solution, wherein hydroxylamine hydrochloride and the mass volume ratio (g/ml) of deionized water are 10:100, then at room temperature in magnetic
The sodium carbonate that power is added with stirring, wherein sodium carbonate and the mass volume ratio (g/ml) of deionized water are 3:100；On the other hand,
By PAN/SiO2Resin and mixed solution are added in three-neck flask, wherein PAN/SiO2The quality volume of resin and deionized water
It is 12:100 than (g/ml)；Installation condensation return mechanism, is then heated to 343K for system, and protect in a water bath under nitrogen atmosphere
Hold 2.5h；It is filtered, after washing and drying, finally obtains the PAO/SiO of synthesis2Resin.
PAO/SiO of the invention2Resin, compared with commercial resins, firstly, the partial size of silica is 75-150 μm, it
There is biggish specific surface area as skeleton, additionally, due to adding pore-foaming agent in the synthesis process, and considerably increase resin
Specific surface area and porosity；Secondly because the expansion rate of commercial resins is larger, and silica is smaller as skeleton expansion rate,
PAO/SiO during absorption2The structure of resin is not easy to be destroyed；Third, it is contemplated that reducing mass transfer distance can make to expand
Scattered speed faster, so selection synthesis PAO/SiO2Resin is more efficiently than commercial resins；4th, due to gallium absorption not only
The surface of resin is occurred over just, while also occurring in the inside of resin, so only successfully synthesizing amidoxim inside resin
Group could more preferably accelerate the rate of reaction, rather than as commercial resins, effective functional group is only distributed in resin
Surface.
Above description has shown and described several preferred embodiments of invention, but as previously described, it should be understood that invention is not
It is confined to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification
And environment, and can be carried out within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
Change.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of invention, then it all should be in the appended power of invention
In the protection scope that benefit requires.
Claims (9)
1. a kind of amidoxim-silica resin preparation method for adsorbing gallium, which comprises the following steps:
Step 1 prepares acrylonitrile-silica resin (PAN/SiO2): using mesoporous silicon dioxide micro-sphere as skeleton, with propylene
Nitrile is raw material, utilizes solution polymerization process synthesis of acrylonitrile-silica resin (PAN/SiO2)；
Amidoxim-silica resin (PAO/SiO of step 2, preparation absorption gallium2): amidoxim function is grafted by amidoximation
Energy group, is modified acrylonitrile-silicon oxide pellets, obtains amidoxim-silica resin (PAO/ of absorption gallium
SiO2)。
2. preparation method according to claim 1, which is characterized in that prepare acrylonitrile-silica in the step 1
Resin (PAN/SiO2) its synthetic route it is as follows:
The following steps are included: selection silica dioxide granule makees skeleton；Silica dioxide granule is put into rotary evaporation flask and is made
It is extracted into negative pressure with vacuum pump, then connects nitrogen cylinder, nitrogen is introduced, vacuumizes；Then by monomer, diluent and initiator it is mixed
Object suck-back is closed to enter in flask；The rotation speed for adjusting Rotary Evaporators, is sufficiently mixed mixture with silica dioxide granule；This
Afterwards, it is heated in silicone oil bath；Obtained silica grafted propylene nitrile resin is cleaned respectively with acetone and water to remove physics
The polymer of attachment, is dried under vacuum, and finally obtains grafted particles PAN/SiO2。
3. preparation method according to claim 2, which is characterized in that the partial size of the silica dioxide granule is 70-150
μm；Pumpdown time is 25-35 minutes.
4. preparation method according to claim 2, which is characterized in that monomer: diluent: the mass ratio of initiator is 90-
110:320-380:0.5-1.5.
5. preparation method according to claim 2, which is characterized in that the monomer is that mass ratio is 20:80-10:90
Divinylbenzene and acrylonitrile；Diluent is the acetophenone and diethyl phthalate that mass ratio is 3:2；Initiator is even
Nitrogen bis-isobutyronitrile.
6. preparation method according to claim 2, which is characterized in that heated in silicone oil bath specifically: be slowly heated to
343K keeps 0.5h-1.5h, and 1.5h-2.5h is then heated at 353K, finally heated to 363K holding 6.5h-7.5h.
7. preparation method according to claim 1, which is characterized in that the amidoxim-of preparation absorption gallium in the step 2
The synthetic route of silica resin is as follows:
The following steps are included: removing ionized water and ethyl alcohol mixing；In a nitrogen atmosphere, by hydroxylamine hydrochloride, it is molten to be dissolved in the mixing
In liquid, the sodium carbonate being then added under magnetic stirring at room temperature, on the other hand, by PAN/SiO2Resin and mixed solution add
Enter into three-neck flask, then system is heated to 343K, and added in a water bath under nitrogen atmosphere by installation condensation return mechanism
Heat；It is filtered, after washing and drying, finally obtains the PAO/SiO of synthesis2Resin.
8. preparation method according to claim 7, which is characterized in that the volume ratio of the deionized water and ethyl alcohol is 1:
1；Hydroxylamine hydrochloride and the mass volume ratio (g/ml) of deionized water are 5:100-10:100, the mass body of sodium carbonate and deionized water
Product is 3:100-5:100 than (g/ml).
9. preparation method according to claim 7, which is characterized in that the PAN/SiO2The matter of resin and deionized water
Measuring volume ratio (g/ml) is 8:100-12:100；The time of water-bath is 2.5h-3.5h.
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