CN106311153B - Order mesoporous silica-base material of a kind of crown ether functionalization SBA-15 type and preparation method thereof - Google Patents
Order mesoporous silica-base material of a kind of crown ether functionalization SBA-15 type and preparation method thereof Download PDFInfo
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- CN106311153B CN106311153B CN201610829279.3A CN201610829279A CN106311153B CN 106311153 B CN106311153 B CN 106311153B CN 201610829279 A CN201610829279 A CN 201610829279A CN 106311153 B CN106311153 B CN 106311153B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/22—Separation by extracting
- B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to ion adsorbing material technical fields, in particular to order mesoporous silica-base material of a kind of crown ether functionalization SBA-15 type and preparation method thereof.The side chain of the crown ether contains amino group；The alkyl group of chlorine substitution is contained on aperture>6nm of the SBA-15, length<1.5 μm in channel, and surface；The mass ratio of SBA-15 and crown ether is (1.5~3): 1.The method of the present invention is simple to operate, practical, and obtained material has high crown ether load factor, and the order of higher meso-hole structure is maintained after synthesis.
Description
Technical field
The present invention relates to ion adsorbing material technical field, in particular to a kind of crown ether functionalization SBA-15 type is order mesoporous
Silica-base material and preparation method thereof.
Background technique
Representative of the nuclear energy as new energy, in the past few decades between, the development advanced by leaps and bounds.It is with reactor
Example, the nuclear power reactor that countries in the world have been commercialized operation is the controllable fission reactor based on uranium isotope, various countries expert
It is dedicated to improving the utilization rate of the heap-type reactor fuel stick.At the same time, controllable fusion reactor is also increasingly subject to every country
Extensive concern.Fusion reaction principle is as follows:
D+T→4He(3.52MeV)+n(14.06MeV)
Tritium needed for the reaction there's almost no in nature, but can be by reacting generation and proliferation as follows:
6Li+n→T+4He+4.8MeV
One of isotope of lithium6Li, abundance is only 7.5% in nature, thermal-neutron capture cross-section 940bar.6Li
It can be used as the material of control rod, absorb neutron for fission reactor, reactor nuclear reaction speed is adjusted, to reach adjusting
The purpose of core power.By above-mentioned reaction it is found that6Li is important nuclear fusion stack fuel, and the tritium in fusion reactor can be made continuous
Proliferation, controllable fusion reaction can also be applied in nuclear aircraft and spaceship in the future.Meanwhile thermonuclear may be implemented in tritium
It reacts (uncontrollable fusion reaction), the development applied to hydrogen bomb.Therefore,6Li is researched and developed to China's nuclear weapon and defense military strength
Promotion has vital effect.
Another isotope of lithium7Li, abundance is 92.5% in nature, and absorption cross-section is minimum, only
0.037bar。7Li both can be used as fusion reactor Core cooling agent and thermally conductive catalyst carrier, can also light-water press water
As pH value and the regulator of B-Li ratio in heap major loop, it is also used as the medium of thorium base fused salt, but in the system7Li is rich
Degree will reach 99.99%, be influenced by its lighter quality, this abundance is extremely difficult to.7Li will not cause because seed is absorbed
Fusion reaction, therefore6Li cannot be present in7In the application system of Li, this is also that the two needs the reason of separating.
Crown ether and its derivative are since finding report, just because it is special to metal ion, especially alkali metal ion
Selective coordination ability, the numerous areas such as extraction chemistry, phase transfer catalysis (PTC), Coordinative Chemistry, ion selectivity carrier by
Concern.From 1979, scholar Jepson used bicyclic crown ether extraction lithium isotope, and since obtaining 1.041 separation, hat
Ether and its derivative play an increasingly important role in the Separation Research field of lithium.
Based on above-mentioned extractant, in conjunction with the separation demand of lithium isotope, people have developed solvent extraction, extraction color in succession
Two class of spectrometry has the separation method of application prospect.Existing scholar has studied crown ether by solvent extraction and divides lithium isotope
From process, and higher separation is obtained, but this method the problems such as that there are organic solvent consumption is big, Waste buildup, simultaneously
Since lithium isotope is relatively light or content in the solution is less, solvent extraction is also and non-best choice.
In contrast, extraction chromatography is caused because of the advantages that its operating process is convenient, equipment is simple and solvent usage is few
The more extensive research interest of researcher.Extraction chromatography is one kind of solid state extraction techniques, will have choosing to target components
The extractant of selecting property binding ability is carried on certain inert solid carrier, and the mobile phase containing target components passes through above-mentioned fixation
The selectivity retention of the component is realized when phase.
Order mesoporous silica-base material is to develop one of more rapid porous material in sloid-liq-uid adsorption system at present, is had
High-ratio surface, thermodynamics and mechanical stability, the pore-size distribution of high unity, pore size be adjustable, high absorption property and can
The advantages that modifying performance.The meso-hole structure of high-sequential constitutes nanoscale channel, and external functionalization group can be grafted on this
The surface in a little channels；High-specific surface area can increase the quantity of these functionalization groups, improve grafting rate；In the synthesis process,
It can be reacted by control, generate short nanochannel, it is in addition not independent between these big apertures, but there are many micro-
Hole, so that diffusion rate is accelerated, to improve the dynamic performance in adsorption process；Material mechanical stability makes adsorption process
Solid phase material come into full contact with liquid phase.These characteristics have order mesoporous silica-base material very in lithium isotope separation field
Big potentiality.
Summary of the invention
The present invention provides order mesoporous silica-base material of a kind of crown ether functionalization SBA-15 type and preparation method thereof, specific skills
Art scheme are as follows:
A kind of order mesoporous silica-base material of crown ether functionalization SBA-15 type, the side chain of the crown ether contain amino group；Institute
State the alkyl group that chlorine substitution is contained on aperture>6nm of SBA-15, length<1.5 μm in channel, and surface；SBA-15 and crown ether
Mass ratio is (1.5~3): 1.
Preferably, the crown ether is 4- amino benzo -12-crown-4,4- amino Benzo15crown5 derivatives 5,4- amino benzo -18-
Crown- 6 or the double phendioxin 8- crown-s 6 of 4- amino, structural formula is followed successively by formula (a)~(d).
A kind of preparation method of the order mesoporous silica-base material of crown ether functionalization SBA-15 type as described above, specific steps
Are as follows:
(1) SBA-15 presoma and catalyst IV are weighed and is ground；
(2) crown ether is dissolved in solvent II, ultrasonic vibration to whole dissolutions；
(3) mixture that step (1) obtains is mixed with the solution that step (2) obtains, and is added and can provides alkali for reaction
The catalyst V of property condition；
(4) it is passed through N2Certain time is to be discharged air, and the oil bath under the conditions of certain temperature；
(5) after reaction, it filters and obtains solid, a certain amount of solvent VI is added, sonic oscillation is washed and is centrifuged repeatedly, directly
The pH value of supernatant liquor is neutrality after to centrifugation, to remove non-grafted crown ether on the surface of the material；
(6) it is dried in vacuo under the conditions of certain temperature, obtains the order mesoporous silicon substrate of the crown ether functionalization SBA-15 type
Material.
Wherein, solvent II is DMF or THF；Catalyst IV is the mixture of carbonate and iodide, for providing alkaline ring
Border；Catalyst V is the hydrochloric acid of generation during the energy neutralization reaction such as triethylamine, organic examination that driving a reaction develops to positive reaction
Agent；Solvent VI is industrial alcohol or dehydrated alcohol.
SBA-15 presoma, crown ether, solvent II, catalyst IV, catalyst V amount ratio be followed successively by (1.5~3g): (1~
2g): (150~300mL): (7~12g): (2~3mL).
In catalyst IV, the mass ratio of carbonate and iodide is (2.5~5): 1.
The condition of the oil bath is 80~100 DEG C, 18~for 24 hours；The process of vacuum drying is in vacuum state 40-50
Under the conditions of DEG C, dry 18~for 24 hours.
The invention has the benefit that the method for the present invention is simple to operate, practical, obtained material has high
Crown ether load factor maintains the order of higher meso-hole structure after synthesis.
Detailed description of the invention
Fig. 1 is the grafting SBA-15 ordered mesoporous silicon of adsorbent material 4- amino benzo-15-crown-5 made from the embodiment of the present invention 1
The infrared spectrogram of sill.
Fig. 2 is the grafting SBA-15 ordered mesoporous silicon of adsorbent material 4- amino benzo-15-crown-5 made from the embodiment of the present invention 1
The schematic diagram of sill.
Fig. 3 is the grafting SBA-15 ordered mesoporous silicon of adsorbent material 4- amino benzo-15-crown-5 made from the embodiment of the present invention 1
The TEM of sill and its presoma SBA-15, SEM photograph；Wherein, it (d) is grafted for adsorbent material 4- amino benzo-15-crown-5
The TEM photo of the order mesoporous silica-base material of SBA-15, (a) are the SEM photograph of order mesoporous silica-base material SBA-15, (b)-(c)
For the TEM photo of order mesoporous silica-base material SBA-15.
Specific embodiment
Embodiment 1:
Weigh 3g presoma SBA-15,10g K2CO3, 4g KI, and it is finely ground with mortar, be transferred to there-necked flask；Weigh 2g's
THF ultrasonic vibration, the dissolution of 100mL is added in 4- amino benzo-15-crown-5；It is all dissolved to 4- amino benzo-15-crown-5, it will
It is transferred to 500mL there-necked flask, adds the triethylamine of 3mL, is passed through nitrogen 5-10min, air is discharged；80 DEG C of oil bath reactions
48h；Solid is transferred to beaker and industrial alcohol or dehydrated alcohol is added, and filters repeatedly；It can be gradually added into previous step
Ionized water, until deionized water all replaces dehydrated alcohol, ultrasonic vibration and the step for be centrifuged, be iteratively repeated, until centrifugation
The pH value of supernatant liquor is neutrality afterwards；70 DEG C of drying solids of baking oven for 24 hours, and are transferred to vacuum oven, use to characterize.
, can be with the microstructure of research material, surface topography by the characterization to material, and modification is verified to the material
Whether material structure has an impact.Before characterization, the material sample prepared is placed in vacuum drying oven (60-70 DEG C) dry 3-5h；It takes
It is 4000-400cm that dried material, which mixes with KBr powder and is placed in spectral region,-1Infrared spectrometer (Nicolet Nexus
470FT-IR spectrometer etc.) in, qualitative analysis material structure can be used to；Elemental analyser (Elementar
Vario EL III etc.) it can be used for quantitative analysis modification in the content of the crown ether group of material surface；Adsorbent material 4- aminobenzene
And the surface topography of the grafting of 15- crown- 5 ordered mesoporous silicon sill SBA-15 can pass through scanning electron microscope (LEO
1530scanning electron microscope etc.) and transmission electron microscope (HT-7700transmission electron
Microscope etc.) judgement.
By Fig. 3 (a) it is found that there is the order mesoporous silica-base material SBA-15 containing Cl group good rod-shaped cylindrical body to have
Ordered meso-porous structure；It is compared with common order mesoporous silica-base material SBA-15, the material containing Cl group has less than 2.0 μm
Short cellular structure, visible apparent two-dimentional hexahedron reticular structure in Fig. 3 (b)；It is orderly big by the visible a large amount of regularity of Fig. 3 (c)
Aperture passage, aperture are about 8nm；By Fig. 3 (d) it is found that due to order mesoporous silica-base material SBA-15 itself have it is good
Physical and chemical stability after Modified with Crown Ether and has not been changed its structure.
As seen from Figure 3, prepared adsorbent material has good ordered mesopore structure；Pass through infrared spectrogram
(Fig. 1) qualitative analysis crown ether has been modified in solid phase material surface；Since adsorbent material itself has the advantage that, it may be assumed that short channel, big
Aperture, enables crown ether group to be modified in large quantities in its surface and inner surfaces of pores, and absorption is calculated by N element content
The grafting rate of material is about 15.8% (~0.56mmol/g), has high crown ether load factor (as shown in table 1).
1 adsorbent material 4- amino benzo-15-crown-5 of table is grafted the order mesoporous silica-base material of SBA-15 and order mesoporous silicon substrate
The elemental analysis value (C, H, N) of material SBA-15
Embodiment 2:
Weigh 1.5g presoma SBA-15,10g K2CO3, 4g KI, and it is finely ground with mortar, be transferred to there-necked flask；Weigh 1g
The double benzo 18- crown-s 6 of 4- amino, DMF ultrasonic vibration, the dissolution of 100mL is added；It is all molten to the double benzo 18- crown-s 6 of 4- amino
Solution, transfers them to 500mL there-necked flask, adds the triethylamine of 2mL, be passed through nitrogen 5-10min, air is discharged；Oil bath 80
DEG C reaction for 24 hours；Solid is transferred to beaker and industrial alcohol or dehydrated alcohol is added, and filters repeatedly；It can be gradually in previous step
Deionized water is added, until deionized water all replaces dehydrated alcohol, ultrasonic vibration and the step for be centrifuged, be iteratively repeated, directly
The pH value of supernatant liquor is neutrality after to centrifugation；70 DEG C of drying solids of baking oven for 24 hours, and are transferred to vacuum oven, to characterize
It uses.
Embodiment 3:
Weigh 3g presoma SBA-15,5g K2CO3, 2g KI, and it is finely ground with mortar, be transferred to there-necked flask；Weigh the 4- of 2g
THF ultrasonic vibration, the dissolution of 100mL is added in amino benzo 12-crown-4；It is all dissolved to 4- amino benzo 12-crown-4, by it
It is transferred to 500mL there-necked flask, adds the triethylamine of 3mL, is passed through nitrogen 5-10min, air is discharged；80 DEG C of oil bath reactions
24h；Solid is transferred to beaker and industrial alcohol or dehydrated alcohol is added, and filters repeatedly；It can be gradually added into previous step
Ionized water, until deionized water all replaces dehydrated alcohol, ultrasonic vibration and the step for be centrifuged, be iteratively repeated, until centrifugation
The pH value of supernatant liquor is neutrality afterwards；70 DEG C of drying solids of baking oven for 24 hours, and are transferred to vacuum oven, use to characterize.
Claims (6)
1. a kind of preparation method of the order mesoporous silica-base material of crown ether functionalization SBA-15 type, which is characterized in that the crown ether
Side chain contains amino group；The alkyl of chlorine substitution is contained on aperture>6nm of the SBA-15, length<1.5 μm in channel, and surface
Group；The mass ratio of SBA-15 and crown ether is (1.5~3): 1；
The specific steps of the preparation method are as follows:
(1) SBA-15 presoma and catalyst IV are weighed and is ground；
(2) crown ether is dissolved in solvent II, ultrasonic vibration to whole dissolutions；
(3) mixture that step (1) obtains is mixed with the solution that step (2) obtains, and catalyst V is added；
(4) it is passed through N2Air, and oil bath is discharged；
(5) after reaction, it filters and obtains solid, solvent VI is added, sonic oscillation is washed and is centrifuged repeatedly, until on after centrifugation
The pH value of layer clear liquid is neutrality；
(6) it is dried in vacuo, obtains the order mesoporous silica-base material of the crown ether functionalization SBA-15 type；
The solvent II is DMF or THF；The solvent VI is industrial alcohol or dehydrated alcohol；
The catalyst IV is the mixture of carbonate and iodide；
The catalyst V is triethylamine.
2. preparation method according to claim 1, which is characterized in that the crown ether is 4- amino benzo -12-crown-4,4-
Amino Benzo15crown5 derivatives 5,4- amino benzo -18- crown- 6 or the double phendioxin 8- crown-s 6 of 4- amino.
3. preparation method according to claim 1, which is characterized in that SBA-15 presoma, crown ether, solvent II, catalyst
IV, catalyst V amount ratio be followed successively by (1.5~3g): (1~2g): (150~300mL): (7~12g): (2~3mL).
4. preparation method according to claim 1, which is characterized in that in catalyst IV, the quality of carbonate and iodide
Than for (2.5~5): 1.
5. preparation method according to claim 1, which is characterized in that the condition of the oil bath be 80~100 DEG C, 18~
24h。
6. preparation method according to claim 1, which is characterized in that the process of vacuum drying is in vacuum state
Under the conditions of 40-50 DEG C, dry 18~for 24 hours.
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| CN107115846B (en) * | 2017-05-11 | 2020-03-27 | 清华大学 | Crown ether immobilized glass fiber material and preparation method thereof |
| CN109260950B (en) * | 2018-11-16 | 2021-06-18 | 中国科学院青海盐湖研究所 | Separation and enrichment method of lithium isotope |
| CN116887917A (en) * | 2021-02-24 | 2023-10-13 | 周学明 | Catalyst and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005254230A (en) * | 2004-02-12 | 2005-09-22 | Tatsuya Suzuki | Isotope separation method, isotope separation apparatus and isotope separation means |
| CN105617979A (en) * | 2016-03-09 | 2016-06-01 | 清华大学 | Modified mesoporous silica adsorbent and preparation method and application thereof |
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2016
- 2016-09-18 CN CN201610829279.3A patent/CN106311153B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005254230A (en) * | 2004-02-12 | 2005-09-22 | Tatsuya Suzuki | Isotope separation method, isotope separation apparatus and isotope separation means |
| CN105617979A (en) * | 2016-03-09 | 2016-06-01 | 清华大学 | Modified mesoporous silica adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "New short-channel SBA-15 mesoporous silicas functionalized with polyazamacrocyclic ligands for selective capturing of palladium ions in HNO3 media";Fengcheng Wu, et al.;《RSC Adv.》;20160707;第6卷;第66537-66547页 |
| "Preparation and Characterization of Polysulfone-graft-4’-aminobenzo-15-crown-5-ether for Lithium Isotope Separation";Feng Yan, et al.;《Ind. Eng. Chem. Res.》;20150317;第54卷;第3473-3479页 |
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