CN104525130A - Method for preparing amidoxime-group ethane bridged bond mesoporous silica - Google Patents

Method for preparing amidoxime-group ethane bridged bond mesoporous silica Download PDF

Info

Publication number
CN104525130A
CN104525130A CN201410853527.9A CN201410853527A CN104525130A CN 104525130 A CN104525130 A CN 104525130A CN 201410853527 A CN201410853527 A CN 201410853527A CN 104525130 A CN104525130 A CN 104525130A
Authority
CN
China
Prior art keywords
bridged bond
silicon dioxide
ethane
dioxide material
ethane bridged
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410853527.9A
Other languages
Chinese (zh)
Other versions
CN104525130B (en
Inventor
王劲松
陆森
熊正为
谢水波
唐振平
徐华
唐小林
杨金辉
李霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanhua University
University of South China
Original Assignee
University of South China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of South China filed Critical University of South China
Priority to CN201410853527.9A priority Critical patent/CN104525130B/en
Publication of CN104525130A publication Critical patent/CN104525130A/en
Application granted granted Critical
Publication of CN104525130B publication Critical patent/CN104525130B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a synthetic method of an amidoxime-group ethane bridged bond mesoporous silica composite material. The method includes two steps that firstly, a cyano-group is led into a silica gel duct of silicon dioxide, and ethane perssad synthesis functional mesoporous silica materials are led into a hole wall through bridged bonds; secondly, amidoxime-group ethane bridged bond mesoporous silica composite material is synthesized on this basis. The synthesis material synthesized through the method has regular mesoporous structures, large specific area, good adsorptive property on uranium and good regenerated adsorptive capacity, so the synthesis material has good application prospects on radioactive wastewater treatment and uranium recovery.

Description

A kind of preparation method of amidoxime group ethane bridged bond mesoporous silicon oxide
Technical field
The invention belongs to organo-mineral complexing functionalization materials synthesis, be specifically related to a kind of preparation method of amidoxime group ethane bridged bond Metaporous silicon dioxide material.
Background technology
At present, Environmental Pollution and Control is global important topic, and along with the development of uranium mining industry, in part producing, process waste liquor and pollutant cause water pollution to environmental emission, makes in waste water containing multiple radionuclide.Human body is subject to internal radiation by drinking contaminant water, brings very large harm to health.Therefore, in the urgent need to a kind of cheap effective method, increasing low concentration uranium-bearing wastewater is administered.Absorption method removes Uranium in Waste Water (VI) the most promising method at present, and wherein maximum to have optionally fiber containing amidoxime groups investigation of materials, though the rate of adsorption of this kind of material is fast, mechanical strength is lower, easily swelling, shortens the service life of material.Therefore, develop a kind of Novel adsorption parting material, make it both have good hydrophily containing on the basis of amidoxime group, there is again higher mechanical strength simultaneously, there is important theory significance and actual application value.
Metaporous silicon dioxide material is because having high-ratio surface sum large pore volume, extremely low density and excellent physicochemical properties and the design feature such as higher heat endurance and strong acid resistance, can not be swelling during use, material surface is rich in abundant silicone hydroxyl, can with containing donor atom and functional group as modified ligand, by silane coupler, organic group is connect skill to its surface, the functional mesoporous silica prepared can efficient adsorption various heavy, is the very promising solid absorbent carrier material of one.Cyano functional group-CN has higher reactivity, and it not only can complexing many kinds of metal ions, also by further reaction, and the derivative activated centre made new advances.Such as be reduced into aldehyde, hydrolysis becomes carboxyl, amidoximation is converted into amidoxime group etc.Therefore cyano group is introduced mesoporous silicon oxide and become study hotspot.Researcher (Fiorilli S, Onida B, Bonelli B, et al. In situ infrared study of SBA-15 functionalized with carboxylic groups incorporated by a co-condensation route. J. Phys. Chem. B, 2005,109 (35): 16,725 16729.) in acid condition, adopt copolycondensation method to synthesize cyano group functionalization SBA-15, and prepare carboxylic acid functional SBA-15 by sulphuric acid hydrolysis.The material of copolymerization method synthesis can be relatively uniform be distributed in the duct of material, but in order to holding structure orderly, the organic group ratio of introducing is lower, and limits the type can selecting organic group.The organic-inorganic hybrid mesoporous material of type (PMOs) built by bridge, organo-functional group is uniformly distributed in skeleton, duct can not be blocked, occupy pore volume, and there is the mechanical strength that flexible organic group can improve material, keep the high-sequential of material also can improve mechanical property, the hydrothermal stability of material can introduce the organic group situation of high level in hole wall under, new research direction has been opened up in the discovery of this material.People start to transfer the functionalized of research material hole wall.(the Burleigh M.C. such as Jayasundera, Jayasundera S., Spector M.S., et al. A new family of copolymers:multifunctional periodic mesoporous organosilicas. Chem. Mater., 2004,16:3-5.) then to have prepared in skeleton the PMOs material simultaneously with phenyl and ethane, first time makes skeleton with difunctional.(the Burleigh M.C. such as Burleigh, Markowitz M.A., Spector M.S., etal.Nanoporous organosilicas:periodic materials synthesized with surfactantemplates in acidic media. J. Phys. Chem. B. 2002,106:9712-9716.) same in alkaline environment, be that structure directing agent has prepared ethane bridged bond with CTAC, the difunctionalization PMOs material containing functional groups such as amino, pyridine or phenyl in duct.The research preparing the earth silicon material of cyano group functionalization ethane bridged bond but rarely has report.Therefore ethane bridged bond is entered Metaporous silicon dioxide material formation, containing amidoxime group ethane bridged bond Metaporous silicon dioxide material, there is certain practical value and innovative significance.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of amidoxime group Metaporous silicon dioxide material, be intended to solve the control complexity that there is the process of radioactivity uranium-containing waste water and exist, inefficient problem.The invention discloses a kind of synthetic method of amidoxime group ethane bridged bond meso-porous titanium dioxide silicon composite, first in silica duct, cyano group is introduced, and in hole wall bridged bond ethane group complex functionality Metaporous silicon dioxide material, then amidoxime group ethane bridged bond SiO 2 mesoporous materials is synthesized on this basis, the well-regulated meso-hole structure of composite tool of synthesis and larger specific area, there are good absorption property and good regenerative adsorption ability to uranium, have a good application prospect in Spent Radioactive water treatment and uranium recovery.
The present invention is achieved in that and first synthesizes cyano group functionalization ethane bridged bond Metaporous silicon dioxide material, and detailed process is as follows: under 40 DEG C of conditions, by a certain amount of surfactant EO 20pO 70eO 20(P123) be dissolved in deionized water and concentrated hydrochloric acid mixed liquor, fully stir, be uniformly dissolved completely to P123, dropwise add a certain amount of coupling agent (3-cyanogen propyl group) triethoxysilane (NPTS) and silicon source ethyl orthosilicate (TEOS) and 1, the mixed solution of 2-bis-(triethoxy is silica-based) ethane (BTSE), and Keep agitation at the same temperature, then obtained mixed liquor is put into reactor thermostatic crystallization at 100 DEG C, the mixture be obtained by reacting is cooled to room temperature, suction filtration, be washed with water to neutrality again, 70 DEG C of vacuum drying, obtaining white powder is cyano group functionalization ethane bridged bond Metaporous silicon dioxide material (P123-CN-PMOs) containing template P123.With apparatus,Soxhlet's containing concentrated hydrochloric acid absolute ethyl alcohol in extract 24 hours, then suction filtration, be washed to neutrality, put into 70 DEG C of dryings, obtain white powder and be cyano group functionalization ethane bridged bond Metaporous silicon dioxide material (CN-PMOs).
Further, the proportioning of materials synthesis described above each material used is P123:H 2: x, wherein (x=molar fraction %)=0.1 ~ 0.4 O:HCl:NPTS:TEOS: BTSE=0.017:166:6:x:(1-x).
Further, in apparatus,Soxhlet's as above put concentrated hydrochloric acid and absolute ethyl alcohol volume ratio be 1:20.
Further, crystallization process as above is thermostatic crystallization 24 hours at 100 DEG C in stainless steel cauldron.
Then on the basis of cyano group functionalization ethane bridged bond Metaporous silicon dioxide material, synthesize amidoxime group ethane bridged bond Metaporous silicon dioxide material, detailed process is as follows:
In 250mL there-necked flask, add a certain amount of hydroxylamine hydrochloride crystal, add the vibration of certain water gaging and dissolve; Subsequently at N 2appropriate anhydrous Na is added under protection 2cO 3, vibration makes to dissolve completely, stirs and be heated to uniform temperature to keep constant temperature.Then add a certain amount of (CN-PMOs), 70 DEG C of isothermal reaction 3h, by sample filtering after having reacted, and be washed till neutrality with ultra-pure water, and till not making potassium permanganate fade, by product in 50 DEG C of vacuum drying, obtain amidoxime group ethane bridged bond mesoporous silicon oxide (AO-PMOs).
Further, each reactant described above is hydroxylamine hydrochloride crystal by amount of substance ratio: cyano group functionalization ethane bridged bond Metaporous silicon dioxide material: natrium carbonicum calcinatum is 2:2:1.
Further, as above tell will at N 2anhydrous Na is added under protection 2cO 3, and at 70 DEG C of isothermal reaction 3h.
Further, amidoxime group ethane bridged bond Metaporous silicon dioxide material described above is used for the absorption of heavy metal uranium.
The amidoxime group ethane bridged bond Metaporous silicon dioxide material of the present invention's synthesis has very high absorption property and selective to radioactive uranium, during embody rule, the initial concentration of uranium controls at 10mg/L, at 30 DEG C, constant temperature oscillation 1 hour under 150r/min, pH controls 4.0 ~ 7.0; During radioactive uranium individualism, amidoxime group ethane bridged bond Metaporous silicon dioxide material can reach 99% to the clearance of uranium, and thus, the present invention also provides the method for above-mentioned Adsorption of Heavy Metals.
Therefore, the present invention has following advantage: the present invention is from the coordination configuration of radioactive uranium, select to uranium have optionally amidoxime group as the organic group of material, select have strong mechanical strength, bigger serface mesoporous silicon oxide as inorganic carrier, adopt hydro-thermal method one-step synthesis bridged bond ethyl group group in hole wall, the cyano group functionalization ethane bridged bond Metaporous silicon dioxide material of cyano group is introduced in duct.Through amidoximation, cyano group is changed into amidoxime group synthesis amidoxime group ethane bridged bond Metaporous silicon dioxide material.By the selective absorption of this materials application in uranium-containing waste water, provide a kind of new method and access for uranium-containing waste water efficiently processes.The present invention be advantageous in that synthetic route is simple, reaction condition is gentle, do not need HTHP, productive rate is high, adding less, and the amidoxime group ethane bridged bond Metaporous silicon dioxide material adopting method provided by the invention to prepare has high absorption property and selective to uranium, there is the rate of adsorption simultaneously fast, adsorbance is large, and the features such as power of regeneration is strong, are applicable to the process of uranium-containing waste water.
Accompanying drawing explanation
Fig. 1 is the synthetic method flow chart of the amidoxime group ethane bridged bond mesoporous silicon oxide that the embodiment of the present invention provides.
Fig. 2 is the nitrogen adsorption-desorption isotherm of the cyano group functionalization ethane bridged bond Metaporous silicon dioxide material that the embodiment of the present invention provides.
Fig. 3 is the pore size distribution curve of the cyano group functionalization ethane bridged bond Metaporous silicon dioxide material that the embodiment of the present invention provides.
Fig. 4 is the stereoscan photograph of the cyano group functionalization ethane bridged bond Metaporous silicon dioxide material that the embodiment of the present invention provides.
Fig. 5 is the infrared spectrogram of the cyano group functionalization ethane bridged bond Metaporous silicon dioxide material that the embodiment of the present invention provides.
Nitrogen adsorption-the desorption isotherm of the amidoxime group ethane bridged bond Metaporous silicon dioxide material that Fig. 6 embodiment of the present invention provides.
The pore size distribution curve of the amidoxime group ethane bridged bond Metaporous silicon dioxide material that Fig. 7 embodiment of the present invention provides.
The stereoscan photograph of the amidoxime group ethane bridged bond Metaporous silicon dioxide material material that Fig. 8 embodiment of the present invention provides.
The infrared spectrogram of the amidoxime group ethane bridged bond Metaporous silicon dioxide material that Fig. 9 embodiment of the present invention provides.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Below in conjunction with drawings and the specific embodiments, application principle of the present invention is further described.
Below in conjunction with example, the invention will be further described, but be not limitation of the present invention:
Embodiment 1: the preparation of cyano group functionalization ethane bridged bond Metaporous silicon dioxide material
The first step, under 40 DEG C of conditions, by 5g surfactant EO 20pO 70eO 20(P123) be dissolved in 150mL ionized water and 25mL concentrated hydrochloric acid mixed liquor, fully stir 2 hours, be uniformly dissolved completely to P123, dropwise add coupling agent (the 3-cyanogen propyl group) triethoxysilane (NPTS) of 4.7mL and 6.9mL silicon source ethyl orthosilicate (TEOS) and 1.8mL1, the mixed solution of 2-bis-(triethoxy is silica-based) ethane (BTSE), and Keep agitation 24 hours at the same temperature, then obtained mixed liquor is put into reactor thermostatic crystallization 24 hours at 100 DEG C, the mixture be obtained by reacting is cooled to room temperature, suction filtration, be washed with water to neutrality again, 70 DEG C of vacuum drying 10 hours, obtaining white powder is cyano group functionalization ethane bridged bond Metaporous silicon dioxide material (P123-CN-PMOs) containing template.24 hours are extracted with apparatus,Soxhlet's (VHCl:VEtOH=1:20) in the 200mL absolute ethyl alcohol containing 10mL concentrated hydrochloric acid, then suction filtration, be washed to neutrality, put into 70 DEG C of dryings 24 hours, obtain white powder and be cyano group functionalization ethane bridged bond Metaporous silicon dioxide material (CN-PMOs).The specific area of this material is 516.66m 2.g -1, aperture is 11.4nm, and pore volume is 0.47 cm 3.g -1, the absworption peak that can obtain 2260nm by infrared spectrum Fig. 5 is attributed to the stretching vibration of C ≡ N, because of bridged bond ethane (-CH 2-CH 2-) existence, still can be observed stronger C-H vibration absorption peak in 2975 and 2931nm place, thus confirm the successful introducing of cyano functional group and bridged bond ethane.Nitrogen adsorption-the desorption curve of this material is as Fig. 2, and pore size distribution curve is shown in Fig. 3, and ESEM is shown in Fig. 4, and infrared spectrogram is as 5.The specific area of this material is 516.66m 2.g -1, aperture is 11.4nm, and pore volume is 0.47cm 3.g -1.
Embodiment 2: the preparation of amidoxime group ethane bridged bond Metaporous silicon dioxide material
In 250mL there-necked flask, add 7.607g hydroxylamine hydrochloride crystal, add the vibration of 22mL water and dissolve; 5.801g anhydrous Na is added subsequently under N2 protection 2cO 3, vibration makes to dissolve completely, stirs and be heated to uniform temperature to keep constant temperature.Then add a certain amount of (CN-PMOs), 70 DEG C of isothermal reaction 3h, by sample filtering after having reacted, and be washed till neutrality with ultra-pure water, and till not making potassium permanganate fade, by product in 50 DEG C of vacuum drying, obtain amidoxime group ethane bridged bond mesoporous silicon oxide (AO-PMOs).The specific area of this material is 463.51m 2.g -1, aperture is 3.7nm, and pore volume is 0.43cm 3.g -1, the nitrogen adsorption-desorption curve of this material is as Fig. 6, and pore size distribution curve is shown in Fig. 7, and ESEM is shown in Fig. 8, and infrared spectrogram is as 9.Cyano group is after amidoximation, and hydroxyl absorption peak fades away, and as Fig. 9 occurs characterizing the C=N key stretching vibration peak of oxime at 1654nm place, the acromion at 1580nm place is the flexural vibrations peak of N-H key, illustrate cyano group successful conversion be amidoxime group.
Embodiment 3:
That gets the 10mg/L of 50mL contains uranium solution in 250mL conical flask, control temperature is 30 DEG C, adjust ph is between 4.0-7.0, take amidoxime group ethane bridged bond Metaporous silicon dioxide material 0.02g prepared by example 2 in above-mentioned conical flask, filter after 150r/min constant temperature oscillation 60min, get the filtrate of 10mL, utilize the residual concentration of Spectrophotometric Determination of Uranium, result shows that adsorption effect is best when pH=6.0, reaches 98.70% to the clearance of uranium.
Embodiment 4
That gets the 10mg/L of 50mL contains uranium solution in 250mL conical flask, control temperature is 30 DEG C, adjust ph is 6.0, take amidoxime group ethane bridged bond Metaporous silicon dioxide material 0.02g prepared by example 2 in above-mentioned conical flask, at 150r/min constant temperature oscillation, take out part solution every 10min and filter, survey the residual concentration of uranium, result shows, is quick adsorption process, reaches 94.16% to uranium clearance at front 10min; 10min ~ 30min, adsorbs more relatively slow, and mainly uranium ion enters the absorption in duct by diffusion; After 30min, absorption change is very slow, shows that being adsorbed on 30min reaches adsorption equilibrium all, reaches 99.04% to uranium clearance.
Embodiment 5:
With reference to alkali metal, alkaline-earth metal content in the seawater, preparation 1%Na +, 1 ‰ K +, 1 ‰ Mg 2+, 1 ‰ Ca 2+with the aqueous solution that the U (VI) of 10mg/L coexists, adsorption experiment is carried out by the method in embodiment 3, adopt the concentration of spectrophotometry residue uranium, result shows that amidoxime group ethane bridged bond Metaporous silicon dioxide material still can reach more than 95% to the clearance of uranium, shows coexisting ion Na +, K +, Mg 2+, Ca 2+less on the impact of materials adsorption uranium, the amidoxime group introduced in Metaporous silicon dioxide material has selective preferably to uranyl ion, and easier and uranyl ion forms complex.
Embodiment 6:
After amidoxime group ethane bridged bond Metaporous silicon dioxide material absorption U (VI), be that reagent carries out wash-out with nitric acid, be specially the agent of 0.2g absorption saturated adsorption and add 50mL, in the salpeter solution of 3mol/L, at room temperature stir desorption certain hour, then suction filtration, deionized water washing are to neutral, for adsorbing next time after drying, result shows, after recycling at 8 times, adsorption rate still can remain on more than 85%, shows that amidoxime group ethane bridged bond Metaporous silicon dioxide material has good regenerative adsorption performance.
The foregoing is only preferred embodiments of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a synthetic method for amidoxime group ethane bridged bond meso-porous titanium dioxide silicon composite, is characterized in that, comprise the steps:
The first step, introduces cyano group in silica duct, and bridged bond ethyl group rolls into a ball complex functionality Metaporous silicon dioxide material in hole wall;
Second step, adds the functional mesoporous earth silicon material that hydroxylamine hydrochloride and (1) step synthesize and reacts and synthesize amidoxime group ethane bridged bond SiO 2 mesoporous materials.
2. synthetic method as claimed in claim 1, is characterized in that the method comprises the steps:
The first step: the preparation of cyano group functionalization ethane bridged bond Metaporous silicon dioxide material: by surfactant EO 20pO 70eO 20(P123) be dissolved in deionized water and concentrated hydrochloric acid mixed liquor, be stirred well to P123 and be uniformly dissolved completely; Dropwise add coupling agent (3-cyanogen propyl group) triethoxysilane (NPTS), silicon source ethyl orthosilicate (TEOS) and 1, the mixed solution of 2-bis-(triethoxy is silica-based) ethane (BTSE), Keep agitation, then obtained mixed liquor is put into reactor constant temperature crystallization, by the mixture cooling be obtained by reacting, suction filtration, then be washed with water to neutrality, it is cyano group functionalization ethane bridged bond Metaporous silicon dioxide material containing template P123 that vacuum drying obtains white powder; Extract in containing the absolute ethyl alcohol of concentrated hydrochloric acid with apparatus,Soxhlet's, then suction filtration, be washed to neutrality, dry, obtain white powder and be cyano group functionalization ethane bridged bond Metaporous silicon dioxide material;
Second step: the preparation of the Metaporous silicon dioxide material of amidoxime group ethane bridged bond: add hydroxylamine hydrochloride crystal in reaction vessel, adds water vibration and dissolves; Subsequently at N 2anhydrous Na is added under protection 2cO 3, vibration makes to dissolve completely, stirs and keeps constant temperature after heating; Then cyano group functionalization ethane bridged bond Metaporous silicon dioxide material is added, N 2the lower isothermal reaction of protection, by sample filtering after having reacted, and is washed till neutrality with ultra-pure water, and till not making potassium permanganate fade, product vacuum is dry, obtain amidoxime group ethane bridged bond mesoporous silicon oxide.
3. synthetic method as claimed in claim 3, is characterized in that the method comprises the steps:
The first step, synthesis cyano group functionalization ethane bridged bond Metaporous silicon dioxide material, detailed process is as follows: under 40 DEG C of conditions, by surfactant EO 20pO 70eO 20(P123) be dissolved in deionized water and concentrated hydrochloric acid mixed liquor, fully stir 2 hours, be uniformly dissolved completely to P123; Coupling agent (the 3-cyanogen propyl group) triethoxysilane (NPTS) dropwise added and silicon source ethyl orthosilicate (TEOS) and 1, the mixed solution of 2-bis-(triethoxy is silica-based) ethane (BTSE), and Keep agitation 24 hours at the same temperature, then obtained mixed liquor is put into reactor thermostatic crystallization 24 hours at 100 DEG C, the mixture be obtained by reacting is cooled to room temperature, suction filtration, be washed with water to neutrality again, 70 DEG C of vacuum drying 12 hours, obtaining white powder is cyano group functionalization ethane bridged bond Metaporous silicon dioxide material containing template P123; With apparatus,Soxhlet's containing concentrated hydrochloric acid absolute ethyl alcohol in extract 24 hours, then suction filtration, be washed to neutrality, put into 70 DEG C of dryings 24 hours, obtain white powder and be cyano group functionalization ethane bridged bond Metaporous silicon dioxide material;
Second step, the basis of cyano group functionalization ethane bridged bond Metaporous silicon dioxide material is synthesized amidoxime group ethane bridged bond Metaporous silicon dioxide material, and detailed process is as follows:
In 250mL there-necked flask, add a certain amount of hydroxylamine hydrochloride crystal, add water vibration and dissolve; Subsequently at N 2appropriate anhydrous Na is added under protection 2cO 3, vibration makes to dissolve completely, stirs and be heated to uniform temperature to keep constant temperature,
Then add cyano group functionalization ethane bridged bond Metaporous silicon dioxide material, 70 DEG C of isothermal reaction 3h, by sample filtering after having reacted, and be washed till neutrality with ultra-pure water, and till not making potassium permanganate fade, by product in 50 DEG C of vacuum drying, obtain amidoxime group ethane bridged bond mesoporous silicon oxide.
4. synthetic method as claimed in claim 2 or claim 3, is characterized in that: described in the first step, the proportioning of each material is P123:H 2: x O:HCl:NPTS:TEOS: BTSE=0.017:166:6:x:(1-x), wherein x=molar fraction %, and be 0.1 ~ 0.4.
5. as claimed in claim 2 or claim 3 synthetic method, is characterized in that: in apparatus,Soxhlet's described in the first step, the volume ratio of concentrated hydrochloric acid and absolute ethyl alcohol is 1:20, and described crystallization is thermostatic crystallization 24 hours at 100 DEG C in stainless steel cauldron.
6. synthetic method as claimed in claim 2 or claim 3, is characterized in that each reactant described in second step is hydroxylamine hydrochloride crystal by amount of substance ratio: cyano group functionalization ethane bridged bond Metaporous silicon dioxide material: natrium carbonicum calcinatum is 2:2: 1.
7. synthetic method as claimed in claim 2 or claim 3, is characterized in that the reaction described in second step is at N 2anhydrous Na is added under protection 2cO 3, and at 70 DEG C of isothermal reaction 3h.
8. the amidoxime group ethane bridged bond Metaporous silicon dioxide material that the synthetic method as described in any one of claim 1-7 obtains.
9. the application of amidoxime group ethane bridged bond Metaporous silicon dioxide material in adsorption uranium as claimed in claim 8, or at process uranium-containing waste water to remove the application in uranium.
10. apply as claimed in claim 9, it is characterized in that: synthesized amidoxime group ethane bridged bond Metaporous silicon dioxide material is used for the absorption of uranium, and during absorption, the initial concentration of uranium controls within 10mg/L, and adsorption time is within 1 hour, adsorption temp is 30 DEG C, and pH controls at 4.0-7.0.
CN201410853527.9A 2014-12-31 2014-12-31 A kind of preparation method of amidoxime group ethane bridged bond mesoporous silicon oxide Expired - Fee Related CN104525130B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410853527.9A CN104525130B (en) 2014-12-31 2014-12-31 A kind of preparation method of amidoxime group ethane bridged bond mesoporous silicon oxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410853527.9A CN104525130B (en) 2014-12-31 2014-12-31 A kind of preparation method of amidoxime group ethane bridged bond mesoporous silicon oxide

Publications (2)

Publication Number Publication Date
CN104525130A true CN104525130A (en) 2015-04-22
CN104525130B CN104525130B (en) 2017-07-14

Family

ID=52840863

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410853527.9A Expired - Fee Related CN104525130B (en) 2014-12-31 2014-12-31 A kind of preparation method of amidoxime group ethane bridged bond mesoporous silicon oxide

Country Status (1)

Country Link
CN (1) CN104525130B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104998590A (en) * 2015-07-23 2015-10-28 南京理工大学 Surface-modified KIT-6 mesoporous material and synthesis method and application thereof
CN105817213A (en) * 2016-05-23 2016-08-03 大连工业大学 Adsorbent based on hollow mesoporous silica, preparing method of adsorbent and application of adsorbent in recycling gold
CN106179271A (en) * 2016-08-05 2016-12-07 四川大学 Hyperbranched Nano diamond of polyamidoxime functionalization and preparation method and application
CN106824101A (en) * 2017-03-14 2017-06-13 浙江大学 A kind of method of the adsorption uranium from seawater
CN106847357A (en) * 2017-02-13 2017-06-13 东莞市联洲知识产权运营管理有限公司 The method of coagulant sedimentation absorption method Combined Treatment radioactivity uranium-containing waste water
CN106902747A (en) * 2017-03-29 2017-06-30 东华理工大学 A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof
CN107043112A (en) * 2017-05-03 2017-08-15 华南理工大学 A kind of improved silica aerogel microball and its preparation method and application
CN109954484A (en) * 2019-04-04 2019-07-02 哈尔滨工程大学 The uranium absorption material and preparation method of mesoporous silica gel particulate load amidoxim polymer
CN112892497A (en) * 2021-01-19 2021-06-04 江苏大学 Preparation method and application of basin-covering type hollow porous polymer microspheres
CN113231048A (en) * 2021-06-23 2021-08-10 东华理工大学 Uranium adsorbent and preparation method and application thereof
CN115025804A (en) * 2022-06-30 2022-09-09 哈尔滨工程大学 Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郭风: "《偕胺肟基介孔二氧化硅的合成及其对铀的吸附性能研究》", 《中国优秀硕士学位论文全文数据库》 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104998590A (en) * 2015-07-23 2015-10-28 南京理工大学 Surface-modified KIT-6 mesoporous material and synthesis method and application thereof
CN105817213A (en) * 2016-05-23 2016-08-03 大连工业大学 Adsorbent based on hollow mesoporous silica, preparing method of adsorbent and application of adsorbent in recycling gold
CN105817213B (en) * 2016-05-23 2018-04-03 大连工业大学 A kind of application of adsorbent based on hollow mesoporous silicon oxide and preparation method thereof and recovery gold
CN106179271A (en) * 2016-08-05 2016-12-07 四川大学 Hyperbranched Nano diamond of polyamidoxime functionalization and preparation method and application
CN106847357A (en) * 2017-02-13 2017-06-13 东莞市联洲知识产权运营管理有限公司 The method of coagulant sedimentation absorption method Combined Treatment radioactivity uranium-containing waste water
CN106824101A (en) * 2017-03-14 2017-06-13 浙江大学 A kind of method of the adsorption uranium from seawater
CN106902747B (en) * 2017-03-29 2019-09-13 东华理工大学 A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof
CN106902747A (en) * 2017-03-29 2017-06-30 东华理工大学 A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof
CN107043112A (en) * 2017-05-03 2017-08-15 华南理工大学 A kind of improved silica aerogel microball and its preparation method and application
CN109954484A (en) * 2019-04-04 2019-07-02 哈尔滨工程大学 The uranium absorption material and preparation method of mesoporous silica gel particulate load amidoxim polymer
CN109954484B (en) * 2019-04-04 2022-03-18 哈尔滨工程大学 Uranium adsorbing material of mesoporous silica gel particle loaded amidoxime polymer and preparation method
CN112892497A (en) * 2021-01-19 2021-06-04 江苏大学 Preparation method and application of basin-covering type hollow porous polymer microspheres
CN113231048A (en) * 2021-06-23 2021-08-10 东华理工大学 Uranium adsorbent and preparation method and application thereof
CN113231048B (en) * 2021-06-23 2022-10-04 东华理工大学 Uranium adsorbent and preparation method and application thereof
CN115025804A (en) * 2022-06-30 2022-09-09 哈尔滨工程大学 Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof
CN115025804B (en) * 2022-06-30 2023-01-31 哈尔滨工程大学 Photocatalytic uranium-captured two-dimensional flaky semiconductor and preparation method thereof

Also Published As

Publication number Publication date
CN104525130B (en) 2017-07-14

Similar Documents

Publication Publication Date Title
CN104525130A (en) Method for preparing amidoxime-group ethane bridged bond mesoporous silica
Naghsh et al. Synthesis of a kaolin-based geopolymer using a novel fusion method and its application in effective water softening
CN104826582A (en) Preparation method of graphene-mesoporous silica aerogel
Jiang et al. Synthesis of pure NaA zeolites from coal fly ashes for ammonium removal from aqueous solutions
Zhang et al. Fly ash-derived mesoporous silica foams for CO2 capture and aqueous Nd3+ adsorption
CN113214480B (en) Synthesis method and adsorption application of cationic framework material
KR101167855B1 (en) Amine-zeolite composites for carbon dioxide absorbing and preparing method for the same
CN106334518B (en) A kind of recyclable magnetic phosphorus adsorbent and preparation method thereof
Liu et al. U (VI) adsorption by one-step hydrothermally synthesized cetyltrimethylammonium bromide modified hydroxyapatite-bentonite composites from phosphate‑carbonate coexisted solution
Zhang et al. Selective carbon dioxide adsorption of ε-Keggin-type zincomolybdate-based purely inorganic 3D frameworks
CN103585975A (en) Preparation method of beta-cyclodextrin/mesoporous attapulgite composite adsorbent
CN106824071A (en) C@SiO of the one kind for Cr (VI) Adsorption2The preparation method of hollow ball
CN102824895A (en) Mesoporous limited functionalized ionic liquid composite material and preparation method and application thereof
CN103691400A (en) Functionalized ionic liquid hybrid mesoporous molecular sieve MCM-48 composite material and preparation method and application thereof
Krajňák et al. Kinetics, thermodynamics and isotherm parameters of uranium (VI) adsorption on natural and HDTMA-intercalated bentonite and zeolite
CN102795631B (en) Method for preparing silicon dioxide aerogel
CN105143104A (en) Method for purifying silane compound or chlorosilane compound, method for producing polycrystalline silicon, and method for regenerating weakly basic ion-exchange resin
Perovskiy et al. Efficient extraction of multivalent cations from aqueous solutions into sitinakite-based sorbents
Perovskiy et al. Sorption of multivalent cations on titanosilicate obtained from natural raw materials. The mechanism and thermodynamics of sorption
CN106902741A (en) A kind of compound adsorbent, preparation method and application for processing uranium-bearing radioactive wastewater
JP2018514495A (en) Method for preparing functionalized geopolymer foam, this functionalized foam and use thereof
Wu et al. Removal of trace radioactive Cs+ by zirconium titanium phosphate: From bench-scale to pilot-scale
Huo et al. Hexacyanoferrate-modified polyvinyl alcohol/graphene oxide aerogel as an efficient and retrievable adsorbent for cesium
CN101670275A (en) Preparation method for three-dimensional ordered macroporous chelating resin
JP2014106181A (en) Radioactive substance sorption agent and manufacturing method of the same

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170714

Termination date: 20181231