CN112691635A - Ordered mesoporous silica adsorbent, preparation method thereof and application thereof in extraction of rhenium - Google Patents
Ordered mesoporous silica adsorbent, preparation method thereof and application thereof in extraction of rhenium Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000003463 adsorbent Substances 0.000 title claims abstract description 116
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052702 rhenium Inorganic materials 0.000 title abstract description 25
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000000605 extraction Methods 0.000 title abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010828 elution Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 239000002262 Schiff base Substances 0.000 abstract description 32
- 239000003513 alkali Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000005576 amination reaction Methods 0.000 abstract description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical group N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 abstract description 2
- 239000013335 mesoporous material Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 125000004427 diamine group Chemical group 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000003335 secondary amines Chemical group 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- -1 amino, aminopropyl Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MNCTVKQVIMVWOE-UHFFFAOYSA-N 2-hydrazinylethylhydrazine Chemical compound NNCCNN MNCTVKQVIMVWOE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NGJWZINEOWULII-UHFFFAOYSA-N n-(propylcarbamothioyl)benzamide Chemical compound CCCNC(=S)NC(=O)C1=CC=CC=C1 NGJWZINEOWULII-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B61/00—Obtaining metals not elsewhere provided for in this subclass
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Abstract
The invention relates to an ordered mesoporous silicon dioxide adsorbent, a preparation method thereof and application thereof in rhenium extraction. The mesoporous material SBA-15 is aminated by adopting a post-grafting method, and the dialdehyde group of glutaraldehyde reacts with an amine reagent and primary amine on the surface of a matrix to prepare the ordered mesoporous silica adsorbent containing schiff alkali bonds. Epichlorohydrin is selected to replace glutaraldehyde to prepare the ordered mesoporous silica adsorbent containing the bis-secondary amine group. The preparation method is simple and convenient, the reaction condition is mild, the use amount of amination reagent is small, the prepared ordered mesoporous silica adsorbent containing schiff base bonds is suitable for high acidity condition, the adsorption capacity to rhenium is strong, effective separation to Re (VII) can be realized, the cycle stability is high, reuse for at least four times can be realized, and the method has practical applicability.
Description
Technical Field
The invention belongs to the technical field of effective adsorption of rhenium and preparation of mesoporous silica adsorption materials, and particularly relates to preparation of an ordered mesoporous silica adsorbent containing schiff alkali bonds or an ordered mesoporous silica adsorbent containing secondary amine groups, and application of the ordered mesoporous silica adsorbent in efficient adsorption of Re (VII).
Background
Rhenium is one of rare scattered elements in the earth crust in nature, and the currently discovered worldwide reserves are only about 2500 tons. Rhenium has excellent catalytic function, high electron emission performance, high temperature resistance and alloy improvement performance, and is an important new metal material, and the problems of rare reserves, sustainable exploitation and the like are always an important reason for limiting the industrial application of rhenium. The molybdenite and the copper concentrate are only two rhenium extracting raw materials with economic value, rhenium can be recycled as a byproduct in the smelting process of the two minerals, and the extraction flow of the rhenium is as follows: firstly, the copper sulfide or molybdenite roasted smoke is leached, and then the extraction is carried out by a solvent extraction method or an ion exchange method, but the method needs to use a large amount of extractant, has long production period, and not only has low recovery efficiency, but also causes serious environmental problems. Therefore, the research personnel are in urgent need to solve the problem of finding an efficient, high-yield, high-purity, economic and environment-friendly method for recovering rhenium.
Currently, methods for extracting rhenium include: activated carbon adsorption, extraction, ion exchange, liquid membrane, redox, precipitation, electrodialysis, etc. The adsorption method is used as the optimal method for extracting rhenium, and has the advantages of low cost, high efficiency, environmental friendliness and the like. The adsorbent is usually made of carbon material, silicon material, resin, biomass, etc. The mesoporous silica material has the advantages of large specific surface area, adjustable aperture, large adsorption capacity, easy modification through chelation or complexation and the like, is an excellent adsorbent, and has wide application prospect in the aspects of wastewater purification, heavy metal and toxic ion adsorption and the like. When the adsorbent is used for adsorbing polar substances or metal ions, hydrophilic substances, namely Lewis base or Lewis acid, are arranged on the pore walls, so that the corresponding adsorbent can be obtained by modifying MCM-41, MCM-48, SBA-15 and the like by using amino, aminopropyl, diamino, ethylenediamine, malonamide, carboxyl, 1-allyl, 1-benzoyl-3-n-propylthiourea, dithiocarbamate, imidazole derivatives and saccharides.
Among the methods of preparing the adsorbent by modifying three kinds of mesoporous silica through one-step method, post-grafting method and periodic mesoporous induced by using an organic precursor, the post-grafting method is the most common method and is the method with the best effect at present. The post-grafting method refers to the process of functionalizing the material by an organic reagent after the mesoporous material is synthesized, and the process mainly comprises (RO)3SiR、ClSiR3Or HN (SiR)3)3And interacting with silanol free on the surface of the silicon dioxide. The great advantage of this method is that the basic structure of the material before and after modification can be retained.
In the related reports of the preparation of the aminated mesoporous silica adsorbent at present, the problems of large use amount of APTES with high price, serious reduction of the specific surface area of the material, damage to the order of the pore structure and even disappearance of the mesopores exist, and the like, so that a base material with low use amount of APTES and high order of the pore structure is urgently needed to be prepared, and the high-efficiency adsorption of Re (VII) is realized by modifying through a post-grafting method.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of an ordered mesoporous silica adsorbent, which has the advantages of small usage amount of APTES (3-aminopropyltriethoxysilane), high order of pore structures of prepared matrix materials, modification, realization of high-efficiency adsorption separation of Re (VII), and high practical value.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of the ordered mesoporous silica adsorbent comprises the following steps:
1) preparation of SBA-15 matrix: adding a template agent P123 into a mixed solution of deionized water and concentrated hydrochloric acid, strongly stirring until the P123 is completely dissolved, slowly dropwise adding a sodium silicate solution, and stirring and reacting the obtained mixture at 40 ℃ for 6 hours; transferring the obtained reactant into a high-pressure kettle, and performing hydrothermal treatment at 95 ℃ for 20 h; filtering, washing, drying, and roasting at 550 deg.C for 4h to obtain SBA-15 matrix;
2) preparation of aminated mesoporous silica material: adding absolute ethyl alcohol into an SBA-15 matrix, introducing nitrogen into the system, dropwise adding APTES under the protection of nitrogen, reacting for 0.5h, dropwise adding deionized water, continuously reacting for 0.5h, performing suction filtration, washing with ethyl alcohol and deionized water, and then placing in an oven at 50 ℃ for drying to obtain an aminated mesoporous silica material;
3) preparing an ordered mesoporous silica adsorbent: adding methanol and amine reagents into the aminated mesoporous silica material, dropwise adding epoxy chloropropane or glutaraldehyde under the stirring condition at the temperature of 60-80 ℃, reacting for 1-4h, cooling to room temperature, performing suction filtration, washing with ethanol, and drying in an oven at the temperature of 50 ℃ to obtain the ordered mesoporous silica adsorbent.
Further, in the preparation method, step 3), when epichlorohydrin is added dropwise, the ordered mesoporous silica adsorbent containing the bis-secondary amine group is obtained.
Further, in the preparation method, step 3), when glutaraldehyde is added dropwise, the ordered mesoporous silica adsorbent containing schiff base bonds is obtained.
In the preparation method, in the step 2), the SBA-15 matrix and APTES are (0.1-0.5) in a molar ratio.
Further, in the above preparation method, in step 3), the amine reagent is methylamine, n-butylamine, n-octylamine, cyclohexylamine, or aniline.
Further, in the preparation method, in the step 3), the molar ratio of the added glutaraldehyde to the nitrogen atoms contained in the aminated mesoporous silica material is glutaraldehyde: N ═ 1 to 25: 1.
The ordered mesoporous silica adsorbent provided by the invention is applied to adsorption separation of Re (VII).
Further, the method is as follows: placing the ordered mesoporous silica adsorbent in a shaking bottle, adding a solution containing Re (VII) metal ions, sealing, shaking up, shaking for adsorption, and filtering to obtain a solid.
Further, the method comprises an elution step of adding an eluent into the solid for elution, shaking the solid at the temperature of 30 ℃ for 12 hours, and filtering the solid.
Further, the eluent has a concentration of 0.59 mol.L-1～2.94mol·L-1NH of (2)3·H2O。
The invention has the beneficial effects that:
1. the adsorbent prepared in the prior art has the defects that the dosage of APTES is large, and the price of APTES is expensive; secondly, the one-step method is to add an amination reagent in the process of forming the silicon dioxide material framework, so that the self-assembly process of the silicon species and the template P123 micelle is influenced, the specific surface area of the material is reduced, the order of the pore structure is damaged, and even the mesopores disappear. According to the invention, ordered mesoporous silica SBA-15 is used as a matrix, the material is aminated by a grafting method, then a dialdehyde group of glutaraldehyde reacts with an amine reagent and primary amine on the surface of the matrix to prepare an adsorbent containing a schiff alkali bond, or epichlorohydrin replaces glutaraldehyde to prepare an adsorbent containing a bis-secondary amine group, the APTES dosage is small, the prepared matrix material has a high pore structure order, and the prepared adsorbent can realize adsorption separation of Re (VII) in a single system and a multi-component system.
2. The preparation method of the invention has the advantages of less consumption of the cross-linking agent APTES in the raw materials and mild reaction conditions.
3. The adsorbent prepared by the invention has good mesoporous ordering of materials, maintains a long-range ordered mesoporous structure, and can efficiently separate and adsorb rhenium from a rhenium solution.
4. The adsorbent containing schiff base bonds prepared by the invention is suitable for useThe catalyst is used under high acidity condition, has stronger adsorption capacity to rhenium, and has maximum adsorption amount of 198.77mg g at pH 2-1The adsorption effect of the adsorbent containing the secondary diamine is ideal from pH 3.
5. The adsorbent containing schiff alkali bonds prepared by the invention can realize selective recovery of Re (VII) from high-concentration Cu (II) wastewater by using 2.94 mol.L-1NH3·H2And O can realize elution, and the adsorption quantity of rhenium is kept stable in four-cycle experiments, so that the silicon dioxide material can be possibly applied to the adsorption of rhenium, and the method has a good application prospect.
In conclusion, the ordered mesoporous silica adsorbent containing schiff base bonds prepared by the invention can effectively adsorb rhenium ions, and has the advantages of small usage amount of raw materials, good adsorbent structure, high adsorption rate and practical practicability.
Drawings
FIG. 1 is a schematic diagram of the synthesis of ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS) and adsorbent containing bis-secondary amine groups (ECH-CHA-0.2N-SS).
FIG. 2 is a transmission electron micrograph of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS).
FIG. 3 is a small angle XRD pattern of ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS) and adsorbent containing bis-secondary amine groups (ECH-CHA-0.2N-SS).
FIG. 4 is a scanning electron micrograph of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS).
FIG. 5A is an IR spectrum of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS).
FIG. 5B is an infrared spectrum of an ordered mesoporous silica adsorbent containing secondary diamine groups (ECH-CHA-0.2N-SS).
FIG. 6 is a graph showing the adsorption capacity of ordered mesoporous silica adsorbents containing schiff base bonds to Re (VII) in a single system under different acidity conditions.
Fig. 7 is an adsorption isotherm of an ordered mesoporous silica adsorbent containing schiff base bonds at pH 2.
FIG. 8 is a graph of the selectivity of ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS) to Re (VII) under different acidity conditions of a mixed system.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to be limiting.
Example 1 ordered mesoporous silica adsorbent (a) ordered mesoporous silica adsorbent containing schiff base bond
The preparation method comprises the following steps:
1. preparation of SBA-15 matrix:
4.0g of template agent P123 is added into a mixed solution of 120mL of deionized water and 20mL of concentrated hydrochloric acid, after strong stirring is carried out until the P123 is completely dissolved, 10.5g of sodium silicate solution is added dropwise under the condition of stirring in a water bath at 40 ℃, and the obtained mixture is stirred and reacted for 6 hours at 40 ℃. Transferring the obtained reactant into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a 95 ℃ oven for hydrothermal treatment for 20h, filtering, washing, drying, roasting at 550 ℃ for 4h, and removing the template agent to obtain white powder which is an SBA-15 matrix.
2. Preparation of aminated mesoporous silica material (0.2N-SS):
preparing an aminated mesoporous silica material by using a post-grafting method: weighing 1g of SBA-15 matrix, placing the SBA-15 matrix in a three-neck flask, adding 80mL of absolute ethyl alcohol, introducing nitrogen into the system, dropwise adding 0.74g of APTES (molar ratio, SBA-15 matrix: APTES is 1:0.2) under the protection of nitrogen, reacting for 0.5h, dropwise adding 20mL of deionized water, continuing to react for 0.5h, after the reaction is finished, performing suction filtration, washing with ethyl alcohol and deionized water for three times respectively, and drying the product in an oven at 50 ℃ to obtain the aminated mesoporous silica material which is named as 0.2N-SS.
3. Different amine reagents are selected to prepare the ordered mesoporous silica adsorbent containing schiff alkali bonds:
3.1) ordered mesoporous silica adsorbents containing schiff base bonds (GA-MMA-0.2N-SS)
0.5g of 0.2N-SS is weighed and placed in a three-neck flask, 15mL of methanol and 0.05mol of methylamine are added into the three-neck flask, 0.05mol of glutaraldehyde (25 w%) is added into the three-neck flask under the condition of stirring at 80 ℃, reaction is carried out for 1h, the powder is changed into reddish brown from white, the mixture is cooled to room temperature, suction filtration and washing are carried out for multiple times by using ethanol, the product is dried in an oven at 50 ℃, an ordered mesoporous silica adsorbent containing schiff alkali bonds is obtained, and the ordered mesoporous silica adsorbent is named as GA-MMA-0.2N-SS, and the preparation process is shown in figure 1.
3.2) ordered mesoporous silica adsorbents containing schiff base bonds (GA-BA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of N-butylamine into the three-neck flask, dropwise adding 0.05mol of glutaraldehyde (25 w%) into the three-neck flask under the condition of stirring at 80 ℃, reacting for 1h, changing the powder from white to reddish brown, cooling to room temperature, carrying out suction filtration, washing with ethanol for multiple times, and drying the product in an oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing schiff alkali bonds, which is named as GA-BA-0.2N-SS.
3.3) ordered mesoporous silica adsorbents containing schiff base bonds (GA-NOA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of N-octylamine into the three-neck flask, dropwise adding 0.05mol of glutaraldehyde (25 w%) into the three-neck flask under the condition of stirring at 80 ℃, reacting for 1h, changing the powder from white to reddish brown, cooling to room temperature, carrying out suction filtration, washing with ethanol for multiple times, and drying the product in an oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing schiff alkali bonds, which is named as GA-NOA-0.2N-SS.
3.4) ordered mesoporous silica adsorbents containing schiff base bonds (GA-CHA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of cyclohexylamine into the three-neck flask, dropwise adding 0.05mol of glutaraldehyde (25 w%) into the three-neck flask under the condition of stirring at 80 ℃, reacting for 1h, changing the powder from white to reddish brown, cooling to room temperature, carrying out suction filtration, washing with ethanol for multiple times, and drying the product in a 50 ℃ oven to obtain the ordered mesoporous silica adsorbent containing schiff alkali bonds, which is named as GA-CHA-0.2N-SS.
3.5) ordered mesoporous silica adsorbents containing schiff base bonds (GA-AN-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of aniline into the three-neck flask, dropwise adding 0.05mol of glutaraldehyde (25 w%) into the three-neck flask under the condition of stirring at 80 ℃, reacting for 1h, changing the powder from white to reddish brown, cooling to room temperature, carrying out suction filtration, washing with ethanol for multiple times, and drying the product in AN oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing schiff alkali bonds, which is named as GA-AN-0.2N-SS.
(II) ordered mesoporous silica adsorbent containing secondary diamine group
The preparation method comprises the following steps:
1. preparation of SBA-15 matrix:
4.0g of template agent P123 is added into a mixed solution of 120mL of deionized water and 20mL of concentrated hydrochloric acid, after strong stirring is carried out until the P123 is completely dissolved, 10.5g of sodium silicate solution is added dropwise under the condition of stirring in a water bath at 40 ℃, and the obtained mixture is stirred and reacted for 6 hours at 40 ℃. Transferring the obtained reactant into a high-pressure reaction kettle, putting the high-pressure reaction kettle into a 95 ℃ oven for hydrothermal treatment for 20h, filtering, washing, drying, roasting at 550 ℃ for 4h, and removing the template agent to obtain white powder which is an SBA-15 matrix.
2. Preparation of aminated mesoporous silica material (0.2N-SS):
preparing an aminated mesoporous silica material by using a post-grafting method: weighing 1g of SBA-15 matrix, placing the SBA-15 matrix in a three-neck flask, adding 80mL of absolute ethyl alcohol, introducing nitrogen into the system, dropwise adding 0.74g of APTES (molar ratio, SBA-15 matrix: APTES is 1:0.2) under the protection of nitrogen, reacting for 0.5h, dropwise adding 20mL of deionized water, continuing to react for 0.5h, after the reaction is finished, performing suction filtration, washing with ethyl alcohol and deionized water for three times respectively, and drying the product in an oven at 50 ℃ to obtain the aminated mesoporous silica material which is named as 0.2N-SS.
3. Selecting different amine reagents to prepare the ordered mesoporous silica adsorbent containing secondary diamine groups:
3.1) ordered mesoporous silica adsorbent containing secondary diamine groups (ECH-MMA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of methylamine into the three-neck flask, dropwise adding 0.05mol of epichlorohydrin into the three-neck flask under the condition of stirring at 60 ℃, reacting for 4 hours, cooling to room temperature, carrying out suction filtration, washing with ethanol for three times, drying a product in an oven at 50 ℃, and obtaining the ordered mesoporous silica adsorbent containing secondary amine groups, namely ECH-MMA-0.2N-SS, wherein the preparation process is shown in figure 1.
3.2) ordered mesoporous silica adsorbents containing diamine bisamino groups (ECH-BA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of N-butylamine into the three-neck flask, dropwise adding 0.05mol of epoxy chloropropane into the three-neck flask under the condition of stirring at 60 ℃, reacting for 4 hours, cooling to room temperature, carrying out suction filtration, washing with ethanol for three times, and drying a product in an oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing secondary amine groups, which is named as ECH-BA-0.2N-SS.
3.3) ordered mesoporous silica adsorbent containing secondary diamine groups (ECH-BA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of N-octylamine into the three-neck flask, dropwise adding 0.05mol of epoxy chloropropane into the three-neck flask under the condition of stirring at 60 ℃, reacting for 4 hours, cooling to room temperature, carrying out suction filtration, washing with ethanol for three times, and drying the product in an oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing the bis-secondary amine group, which is named as ECH-NOA-0.2N-SS.
3.4) ordered mesoporous silica adsorbents containing diamine bisamino groups (ECH-CHA-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of cyclohexylamine into the three-neck flask, dropwise adding 0.05mol of epoxy chloropropane into the three-neck flask under the condition of stirring at 60 ℃, reacting for 4 hours, cooling to room temperature, carrying out suction filtration, washing with ethanol for three times, and drying the product in an oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing secondary amine groups, which is named as ECH-CHA-0.2N-SS.
3.5) ordered mesoporous silica adsorbents containing diamine groups (ECH-AN-0.2N-SS)
Weighing 0.5g of 0.2N-SS, placing the 0.5g of 0.2N-SS in a three-neck flask, adding 15mL of methanol and 0.05mol of aniline into the three-neck flask, dropwise adding 0.05mol of epoxy chloropropane into the three-neck flask under the condition of stirring at 60 ℃, reacting for 4 hours, cooling to room temperature, carrying out suction filtration, washing with ethanol for three times, and drying the product in AN oven at 50 ℃ to obtain the ordered mesoporous silica adsorbent containing secondary amine groups, which is named as ECH-AN-0.2N-SS.
(III) characterization
1. FIG. 2 is a transmission electron micrograph of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS), in which a is a substrate SBA-15; b is 0.2N-SS; c is GA-MMA-0.2N-SS. As can be seen from fig. 2, the adsorbent exhibits a very regular ordered mesostructure regardless of the step to which the modification is carried out.
2. FIG. 3 is a small angle XRD pattern of ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS) and adsorbent containing bis-secondary amine groups (ECH-CHA-0.2N-SS). As can be seen from FIG. 3, the adsorbent has good long-range order, and the order of the mesopores of the adsorbent is not influenced by the process of introducing amino groups into the matrix by the cross-linking agent.
3. FIG. 4 is a scanning electron micrograph of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS). In the figure, a-b is a substrate SBA-15; c-d in the figure are 0.2N-SS; in the figure, e-f is GA-MMA-0.2N-SS; in the figure, g-h is ECH-CHA-0.2N-SS. As can be seen from FIG. 4, the overall morphology of the adsorbent is a long-strip rod-like structure with a smooth surface.
4. FIG. 5A is an IR spectrum of an ordered mesoporous silica adsorbent containing schiff base bonds (GA-MMA-0.2N-SS), wherein a is a substrate SBA-15; in the figure, b is 0.2N-SS; in the figure, c is GA-MMA-0.2N-SS; in the figure, d is GA-BA-0.2N-SS; panel e is GA-NOA-0.2N-SS.
FIG. 5B is an infrared spectrum of an ordered mesoporous silica adsorbent containing secondary diamine groups (ECH-CHA-0.2N-SS), wherein f is the substrate SBA-15; g in the figure is 0.2N-SS; in the figure, h is ECH-MMA-0.2N-SS; in the figure, i is ECH-BA-0.2N-SS; in the figure, j is ECH-NOA-0.2N-SS; in the figure, k is ECH-CHA-0.2N-SS; in the figure, l is ECH-AN-0.2N-SS. As can be seen from B in FIG. 5A and g in FIG. 5B, the amination reagent was successfully grafted onto the substrate. In FIG. 5A, the lines (c), (d), (e) show the appearance of-CH3Asymmetric and symmetric stretching vibration peak and-CH of3The bending vibration peak of (a) is because primary amine contains methyl, and it is proved that glutaraldehyde and primary amine are both connected to the surface of the adsorbent through C ═ N, indicating that mesoporous silica adsorbent containing schiff base bond is successfully prepared.
Example 2 adsorption Performance of ordered mesoporous silica adsorbents for Re (VII) at different acidity conditions
The method comprises the following steps: 10mg of mesoporous silica adsorbent containing schiff base bonds (or ordered mesoporous silica adsorbent containing diamine groups) is placed in a shaking bottle, and then 20 mg.L of different acidity concentrations are respectively added-1After sealing and shaking up, the shaking bottle was placed in a constant temperature shaker, shaken at 180rpm at 30 ℃ for 12 hours, filtered, and the concentration of metal ions in the filtrate was measured with an ultraviolet spectrophotometer.
FIG. 6 is a graph showing the adsorption capacity of ordered mesoporous silica adsorbents containing schiff base bonds to Re (VII) in a single system under different acidity conditions. It can be seen that the adsorbents GA-MMA-0.2N-SS, GA-BA-0.2N-SS, GA-NOA-0.2N-SS, GA-CHA-0.2N-SS, and GA-AN-0.2N-SS in example 1 all reached the highest adsorption rates at pH 2, which were 86%, 84%, 58%, and 24% in this order. And the adsorption rate tends to decrease when the acidity is too high or too low.
Meanwhile, the adsorption capacity of the ordered mesoporous silica adsorbent containing secondary diamine groups on Re (VII) in a single system under different acidity conditions is also analyzed. The ECH-MMA-0.2N-SS, ECH-BA-0.2N-SS, ECH-NOA-0.2N-SS, ECH-CHA-0.2N-SS, ECH-AN-0.2N-SS prepared in example 1 reached the highest adsorption rate at pH 5, but were lower overall by 29%, 63%, 77%, 50% and 20% in this order relative to the ordered mesoporous silica adsorbent containing schiff base bonds.
Example 3 adsorption isotherm of ordered mesoporous silica adsorbents for adsorbing Re (VII)
The method comprises the following steps: weighing 10mg of mesoporous silica adsorbent containing schiff base bonds (or ordered mesoporous silica adsorbent containing di-secondary amine groups) and placing the mesoporous silica adsorbent containing schiff base bonds (or ordered mesoporous silica adsorbent containing di-secondary amine groups) into an oscillation bottle, adding 5mL of rhenium solutions with different concentrations, adjusting the pH to be 2, oscillating the solution for 24 hours under the condition of 303K, collecting filtrate after adsorption equilibrium, and detecting the concentration of Re (VII) in the filtrate by using an ultraviolet spectrophotometer. The results are shown in FIG. 7.
Fig. 7 is an adsorption isotherm of an ordered mesoporous silica adsorbent containing schiff base bonds at pH 2. ByAs can be seen from FIG. 7, the saturated adsorption amounts of GA-MMA-0.2N-SS, GA-BA-0.2N-SS, GA-NOA-0.2N-SS, GA-CHA-0.2N-SS and GA-AN-0.2N-SS were 198.77mg g in that order-1、149.79mg·g-1、150.17mg·g-1、174.96mg·g-1、12.68mg·g-1(ii) a As can be seen, the highest amount of Re (VII) adsorption was obtained for GA-MMA-0.2N-SS in example 1.
Meanwhile, the adsorption isotherm of the ordered mesoporous silica adsorbent containing the diamine group under the condition of pH 2 is analyzed. The saturated adsorption amounts of ECH-MMA-0.2N-SS, ECH-BA-0.2N-SS, ECH-NOA-0.2N-SS, ECH-CHA-0.2N-SS, and ECH-AN-0.2N-SS prepared in example 1 were, in order, 30.08mg g-1、119.64mg·g-1、124.68mg·g-1、122.86mg·g-1、83.35mg·g-1It can be seen that the saturated adsorption capacity of the adsorbent containing secondary diamine groups is lower than that of the adsorbent containing schiff base bonds in the examples.
Example 4 Selective adsorption Effect of ordered mesoporous silica adsorbents containing schiff base bonds on rhenium at different acidity
The method comprises the following steps: 10mg of GA-MMA-0.2N-SS adsorbent was put in a shaker, 5mL of metal mixed solutions having different concentrations and kinds were added, respectively, and after shaking in a sealed state, the shaker was put in a constant temperature shaker, shaken at 30 ℃ for 12 hours at 180rpm, filtered, and the concentration of each metal ion in the filtrate was measured by ICP, as shown in FIG. 8 and tables 1 and 2.
TABLE 1 adsorption rate of adsorbent to each metal ion in solution under different acidity conditions
TABLE 2 Selectivity factors for Re (VII) for adsorbents at different acidity conditions
As can be seen from FIG. 8 and tables 1 and 2, GA-MMA-0.2N-SS has a high adsorption rate to Re (VII) at pH 1.5-3.0, and the adsorption rate can reach 85% or more. In the acidity range of pH 1.0-1.5, the adsorbent can realize effective separation of Re (VII) in the mixed solution.
Example 5 elution Effect of different eluents on mesoporous silica adsorbents containing schiff base bonds adsorbing rhenium (selection of eluent)
The method comprises the following steps: 10mg of GA-MMA-0.2N-SS as an adsorbent was put in a shaker, and 200 mg. L was added thereto-1And (3) 10mL of rhenium solution, filtering after adsorption balance, collecting filtrate to be tested, then respectively eluting the adsorbed adsorbent with 10mL of different eluents, oscillating for 12h at the temperature of 30 ℃, filtering, and collecting the filtrate to be tested. The results are shown in Table 3.
TABLE 3 elution experiment of adsorbent GA-MMA-0.2N-SS
As is clear from Table 3, the concentration was 2.94 mol. L-1The ammonia water has the best analysis effect on GA-MMA-0.2N-SS adsorbing rhenium, and can reach 99.36%. The preferred eluent of the invention is 2.94 mol.L-1NH3·H2O
(II) cycle experiment
100mg of GA-MMA-0.2N-SS adsorbent was placed in a shaker, and 50 mg. L was added thereto-1Is carried out by filtering after adsorption equilibrium, collecting filtrate to be tested, and then using 100mL eluent 2.94 mol.L-1The ammonia water is used for eluting the adsorbent, the filtrate is collected to be tested after the elution is finished, and the process is continuously repeated by using the adsorbent. The results are shown in Table 4.
TABLE 4 GA-MMA-0.2N-SS Cyclic adsorption Performance
As can be seen from table 4, the adsorbent adsorption performance was stable over four cycles.
Claims (8)
1. The preparation method of the ordered mesoporous silica adsorbent is characterized by comprising the following steps:
1) preparation of SBA-15 matrix: adding a template agent P123 into a mixed solution of deionized water and concentrated hydrochloric acid, strongly stirring until the P123 is completely dissolved, slowly dropwise adding a sodium silicate solution, and stirring and reacting the obtained mixture at 40 ℃ for 6 hours; transferring the obtained reactant into a high-pressure kettle, and performing hydrothermal treatment at 95 ℃ for 20 h; filtering, washing, drying, and roasting at 550 deg.C for 4h to obtain SBA-15 matrix;
2) preparation of aminated mesoporous silica material: adding absolute ethyl alcohol into an SBA-15 matrix, introducing nitrogen into the system, dropwise adding APTES under the protection of nitrogen, reacting for 0.5h, dropwise adding deionized water, continuously reacting for 0.5h, performing suction filtration, washing with ethyl alcohol and deionized water, and then placing in an oven at 50 ℃ for drying to obtain an aminated mesoporous silica material;
3) preparing an ordered mesoporous silica adsorbent: adding methanol and amine reagents into the aminated mesoporous silica material, dropwise adding epoxy chloropropane or glutaraldehyde under the stirring condition at the temperature of 60-80 ℃, reacting for 1-4h, cooling to room temperature, performing suction filtration, washing with ethanol, and drying in an oven at the temperature of 50 ℃ to obtain the ordered mesoporous silica adsorbent.
2. The process according to claim 1, wherein in the step 2), the ratio of SBA-15 substrate to APTES is 1 (0.1 to 0.5) in mol%.
3. The method according to claim 1, wherein in step 3), the amine reagent is methylamine, n-butylamine, n-octylamine, cyclohexylamine, or aniline.
4. The preparation method according to claim 1, wherein in the step 3), the molar ratio of the glutaraldehyde to the nitrogen atoms contained in the aminated mesoporous silica material is glutaraldehyde: N ═ 1-25: 1.
5. Use of the ordered mesoporous silica adsorbent prepared according to any one of claims 1 to 4 for adsorptive separation of re (vii).
6. Use according to claim 5, characterized in that the method is as follows: placing the ordered mesoporous silica adsorbent in a shaking bottle, adding a solution containing Re (VII) metal ions, sealing, shaking up, shaking for adsorption, and filtering to obtain a solid.
7. The use of claim 6, comprising an elution step of adding an eluent to the solid for elution, shaking at 30 ℃ for 12 hours, and filtering.
8. Use according to claim 7, wherein the eluent is at a concentration of 0.59 mol-L-1～2.94mol·L-1NH of (2)3·H2O。
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