CN103406114A - Preparation method and application of adsorbent for high-level wastewater treatment - Google Patents
Preparation method and application of adsorbent for high-level wastewater treatment Download PDFInfo
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- CN103406114A CN103406114A CN2013102915316A CN201310291531A CN103406114A CN 103406114 A CN103406114 A CN 103406114A CN 2013102915316 A CN2013102915316 A CN 2013102915316A CN 201310291531 A CN201310291531 A CN 201310291531A CN 103406114 A CN103406114 A CN 103406114A
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Abstract
The invention discloses a preparation method and application of an adsorbent for high-level wastewater treatment. The preparation method comprises the following steps: (1) preparing SiO2 alcosol by adopting a split-phase method, and preparing TiO2 alcosol by adopting a sol-gel method; (2) separately ageing the SiO2 alcosol and the TiO2 alcosol for 20-28 hours, then dropwise adding the SiO2 alcosol to the TiO2 alcosol in proportion, evenly mixing, adding formamide and react to obtain SiO2/TiO2 alcogel; drying at normal pressure after carrying out post-treatment on the alcosol, so as to obtain composite modified SiO2/TiO2 aerogel; and (3) adding the composite modified SiO2/TiO2 aerogel to high-level wastewater to realize absorption. The adsorbent prepared by the preparation method has a clear cavernous structure, high mechanical property, high thermodynamic stability, high chemical stability, high adsorption capacity and high adsorption selectivity.
Description
Technical field
The present invention relates to that radioactive liquid waste is processed, the removal of heavy metal ion and nuke rubbish element the field such as solidify, relate in particular to a kind of preparation method and application of putting the adsorbent of wastewater treatment for height.
Background technology
In order to solve the world energy sources crisis, nuclear energy has become the developing direction of new forms of energy in the quite a long period from now on.High activity liquid waste, i.e. high-level liquid waste (HLLW), be mainly derived from the spentnuclear fuel of not doing post processing and the extract of spentnuclear fuel post processing the first circulation, or other extraction cycle concentrates.It is strong that they have radioactivity; Toxicity is large, long half time; Heat generation rate is high; Acid strong, the characteristics that corrosivity is large, under self high radiation field effect, can produce H
2, CO, CH
4, C
2H
6, C
2H
4.Mainly contain more than 200 kind of isotope of 30 multiple elements, wherein radioactive nucleus have tens kinds, and the half-life elder surpasses 1,000,000 years, comprises the fission product more than 99%, the actinides such as the trace uranium be not recovered, plutonium, and most of transuranic element and cladding materials.The process that nuclear energy develops will inevitably produce a large amount of radwastes, if these high activity liquid wastes can not get effectively processing and settling, the ecological environment harm that will certainly depend on for existence to the mankind, finally affect the Sustainable Development and Utilization of nuclear energy.
The characteristics of high activity liquid waste have determined the potential hazard that it is huge, how fast and effeciently to process a large amount of radioactive liquid wastes, are the difficult problems that current various countries face.At present, in the world the processing method of high activity liquid waste is mainly contained to two kinds: solidification method with separate the transmuting method.
Glass solidification has the poisonous gas product; The radioactive elements such as plutonium are not separated, and toxicity is larger, and nuclear proliferation and core terror have a big risk; There are the problems such as criticality safety and neutron shield, are only applicable to middle cool waste, can not solidifying for high-level waste.The solidifying requirements of high activity liquid waste is selected the very high solidification matrix of stability, contains for a long time these nucleic.
Separating the transmuting method separates the transuranic element in high activity liquid waste and long-lived fission product by Chemical Decomposition, fuel made element or target spare send in reactor or accelerator, by nuclear reaction, make it transmuting and become short-lived nuclide or stable element, but its equipment requirement is high, cost is large and efficiency is not high.
From composite factors such as economy, environment, consider, separate toxicity and long-term hazards effect that solidification method also can reduce high activity liquid waste, reduce the volume of the waste liquid that needs dark geological disposal, compare the separation transmuting and more save disposal costs, taking full advantage of resource, is a kind of more promising processing method.The method for separating and processing of high activity liquid waste mainly contains extraction, chromatograph, absorption, ion-exchange and high-temperature electrolysis purifying method, distillation volatilization and laser induced partition method etc.Wherein, absorption method is a kind of important chemistry, physical method, have efficient, cost is low and the extensive advantage such as be suitable for, and can greatly reduce the volume of high activity liquid waste, has been widely used in the removal of heavy metal ion in the aqueous solution and the processing of nuke rubbish element.If go out actinides and long-life fission element from adsorbing separation high activity liquid waste, it is further solidified, dark geological disposal, the low radioactive waste liquid produced after processing simultaneously, carry out shallow ground disposal or earth's surface and dispose, just can be reduced to minimum degree to the radiological hazard that may cause biological and environment.
Along with the experimental technique of sorbing material form, kind, absorption and enriching constantly of research means, and the use of combining of other technologies and adsorption technology, the absorption subject is developed rapidly.The research of the absorption property of current various ABSORBENTS ABSORPTION metal ion and nuke rubbish ion, mainly be included in different adsorption conditionses, as under the conditions such as adsorption temp, adsorption time, original metal ion concentration, adsorbent content, pH value and various interfering ions on the impact of its adsorption capacity, and the research of the dynamics of adsorption process, thermodynamic study and adsorption isotherm line model, possible adsorption mechanism is proposed.According to the adsorbent source, can be divided into natural adsorbent and two kinds, artificial adsorbent.Natural adsorbent mainly refers to plant waste, microorganism and the clay minerals such as various natural zeolite with cavernous structure, aluminium oxide that the nature reserves are abundant.Synthetic adsorbent is mainly the inorganic material such as various zeolites, active carbon, mesopore molecular sieve, porous silica and titanium oxide gel.
The existing adsorbent of putting wastewater treatment for height, frame strength is lower, easily cracking is broken, the liquid-vapor interface produced in gel when dry will cause in hole forming concave meniscus, the surface tension of concave meniscus makes gel shrinkage cracking significantly in dry run, destroyed the network structure of gel, thereby applied limited.
Summary of the invention
The invention provides a kind of preparation method and application of putting the adsorbent of wastewater treatment for height, the adsorbent cavernous structure that the present invention prepares is clear, and mechanical performance is high, and thermodynamics, chemical stability are high, and have high-adsorption-capacity and adsorptive selectivity.
A kind of preparation method of putting the adsorbent of wastewater treatment for height, comprise the steps:
(1) adopt split-phase method to prepare SiO
2Alcosol, adopt sol-gel process to prepare TiO
2Alcosol;
(2) by described TiO
2Alcosol and SiO
2Alcosol is ageing 20～28h respectively, then by the SiO after ageing
2Alcosol splashes into the TiO after ageing in proportion
2In alcosol, add formamide after mixing, reaction obtains SiO
2/ TiO
2Alcogel, to described SiO
2/ TiO
2Alcosol carries out post processing, and constant pressure and dry obtains composite modified SiO
2/ TiO
2Aeroge.
In order further to strengthen the absorption property of adsorbent, at adsorbent surface rhetorical function group, that is: when in step (2), adding formamide, add coating material.
Described formamide is as the gel flocculation aid, addition with preparation TiO
2The volume ratio of the Butyl Phthalate of alcosol is counted 0.05～0.1:1.0.
As preferably, described coating material is
Solution, silica-based quaternized parting material, nitrogen arsine III or diethyl pentetic acid.
The addition of described coating material and TiO
2Alcosol and SiO
2The ratio of the molten cumulative volume of alcohol is 0.2～1.5:1, more preferably 0.8～1.2:1.
Described silica-based quaternized parting material adopts following method synthetic:
Take the 5g plural gel, under room temperature, add the diformazan benzo to be uniformly mixed 20min, add the excess chlorine MTMS, 80 ℃ of stirring and refluxing reaction 6h of constant temperature, use the acetone washing and drying, obtains containing the silica gel alkylation intermediate of chloromethyl;
Take the 4g intermediate, in dioxane, soak 24h, after add excessive trioctylphosphine tertiary amine, stirring reaction 48h under room temperature, and use successively dioxane, 2mol/LNaOH solution washing, finally use the deionized water cyclic washing extremely without chlorion, 50 ℃ of drying under reduced pressure 48h, obtain silica-based quaternized parting material.(reference literature " and Li Huibo, leaf Guoan, Wang Xiaorong etc. absorption property and the mechanism research [J] of silica-based quaternized parting material to Pu (IV). nuclear and radiochemistry, 2010,32 (2): 65-69. " in disclosed preparation method)
Described split-phase method prepares SiO
2The detailed process of alcosol is as follows:
Under stirring condition, polyethylene glycol is dissolved in aqueous hydrochloric acid solution, continue stirring polyethylene glycol is uniformly dissolved, in polyglycol solution, add ethyl orthosilicate, continue to stir the even SiO of acquisition
2Colloidal sol, add expoxy propane and get final product.
The mass volume ratio of described polyethylene glycol (PEG), ethyl orthosilicate (TEOS), aqueous hydrochloric acid solution and expoxy propane (PO) is: 1-3g:10-20mL:20-50mL:4-10mL.
The concentration of described hydrochloric acid solution is in 0.01～0.1moL/L.
The present invention utilizes the oligomer polymerization that phase-splitting is incorporated in sol-gel transition abreast, obtains the cavernous structure of co-continuous.Use ethyl orthosilicate (TEOS) as the organosilicon source, average viscosity average molecular weigh is that 10,000 polyethylene glycol (PEG) is induced phase-splitting as non-ionic surface active agent.
In the process that the silicon oligomer is grown up, part PEG chain by Hydrogen Binding Adsorption in its surface, is accompanied by the carrying out of this absorption, and surface has non-type state silicon polymer and the compatibility between solvent that hydrogen bond is connected constantly to reduce.Control suitable PEG molecular weight and addition, can make solution before sol-gel transition, be separated into different two-phases.Along with the change of PEG content in colloidal sol, gel structure changes, and is in fact the result of vying each other between phase process and sol-gel transition.Usually, the co-continuous that phase-splitting forms is a temporary stable state mutually, if now this structure is solidified, under capillary driving, the Ostwald maturing process can occur, and continuous two meet towards the spherical transformation of surface tension minimum.If when phase-splitting produced the two-phase of co-continuous, parallel generation sol-gel transition, can preserve this structure; Wherein contain solvent more one in dry run, will form because of the volatilization of solvent phase continuous hole.
Before if sol-gel transition occurs in phase process, now phase-splitting has little time fully to carry out, and will form the block structure in few hole; Otherwise after if sol-gel transition occurs in phase process, what phase-splitting formed two meets and be transformed into spheric granules and be cured, the final pattern obtained is the ball particle heaped-up.In the present invention, pass through to control each response parameter in the split-phase method preparation process, make after sol-gel transition occurs in phase process as much as possible, two of phase-splitting formation is met and is transformed into spheric granules and is cured, and making the final pattern obtained is the ball particle heaped-up.
In the present invention before mixing, to SiO
2Alcosol and TiO
2Alcosol all carries out ripening, and mixed pattern is more stable, and ageing process improves pore passage structure, forms comparatively perfect gel network structure.
Described sol-gel process prepares TiO
2The detailed process of alcosol is as follows:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B, under strong agitation, solution B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol, still aging at normal temperatures.Add formamide to improve pore passage structure, form fairly perfect gel network structure.
Wherein, the volume ratio of described butyl titanate, absolute ethyl alcohol, acetic acid and redistilled water is 10-20:40-70:3-10:4-10.
Last handling process described in step (2) is: by SiO
2/ TiO
2Alcogel is first used soaked in absolute ethyl alcohol 20～25h under 55～65 ℃, after washing, again under 55～65 ℃, first use soaked in absolute ethyl alcohol 20～25h, then with ethanolic solution and the absolute ethyl alcohol of ethyl orthosilicate, repeats above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel dry 65～75h in 65～75 ℃ of baking ovens namely obtains SiO
2/ TiO
2Aeroge.
Most preferably, by the SiO obtained
2/ TiO
2Alcogel is first processed by soaked in absolute ethyl alcohol under 60 ℃, remove moisture content unnecessary in alcogel with displacement, repeats once, then with ethanolic solution and the absolute ethyl alcohol of ethyl orthosilicate, repeats above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.
SiO described in step (2)
2Alcosol and TiO
2The silicon titanium mol ratio of alcosol is 1:1.By control, prepare SiO
2The raw material ethyl orthosilicate of alcosol and preparation TiO
2The volume ratio of the raw material butyl titanate of alcosol is controlled, ethyl orthosilicate and butyl titanate all directly adopt commercially available analysis net product, while generally the volume ratio of ethyl orthosilicate and butyl titanate being controlled to 1:1, in preparation-obtained product, silicon titanium mol ratio is 1:1.
The present invention also provides a kind of high processing method of putting wastewater treatment, comprises the steps:
(1) adopt split-phase method to prepare SiO
2Alcosol, adopt sol-gel process to prepare TiO
2Alcosol;
(2) by described TiO
2Alcosol and SiO
2Alcosol is ageing 20～28h respectively, then by the SiO after ageing
2Alcosol splashes into the TiO after ageing in proportion
2In alcosol, add formamide after mixing, reaction obtains SiO
2/ TiO
2Alcogel, to described SiO
2/ TiO
2Alcosol carries out post processing, and constant pressure and dry obtains composite modified SiO
2/ TiO
2Aeroge.
(3) by described composite modified SiO
2/ TiO
2Aeroge is added to height and puts in waste water, carries out adsorption treatment.
Described adsorption time is 70～180h.
Described adsorbent dosage is 2～10g/L waste water.
Adsorbent after adsorption treatment is cured to processing (cold moudling and heat treatment), shallow ground disposal.
If go out actinides and long-life fission element from adsorbing separation high activity liquid waste, it is further solidified, dark geological disposal, the low radioactive waste liquid produced after processing simultaneously, carry out shallow ground disposal or earth's surface and dispose, just can be reduced to minimum degree to the radiological hazard that may cause biological and environment.From composite factors such as economy, environment, consider, separate toxicity and long-term hazards effect that solidification method also can reduce high activity liquid waste, reduce the volume of the waste liquid that needs dark geological disposal, compare the separation transmuting and more save disposal costs, taking full advantage of resource, is a kind of more promising processing method.
Compared with prior art, originally have following beneficial effect:
Absorption method is widely used, and has advantages of a lot of uniquenesses for the treatment of radioactive liquid waste.Existing research work about adsorbent shows, current adsorption technology exists cost high, and preparation is complicated, or adsorption capacity is lower, without shortcomings such as adsorptive selectivities.Conventional SiO
2/ TiO
2The frame strength of gel rubber material is lower, easily cracking is broken, and the liquid-vapor interface produced in gel when dry will cause in hole forming concave meniscus, and the surface tension of concave meniscus makes gel shrinkage cracking significantly in dry run, destroyed the network structure of gel, thereby applied limited.
SiO prepared by this law
2/ TiO
2Aeroge is by nanometer SiO
2And TiO
2Mutually disperse the mesoporous solid material be composited, has very high specific area, the cavernous structure of its co-continuous makes adsorbate can enter smoothly the inner surface of porous adsorbent, guarantee the higher rate of adsorption, cavernous structure is clear simultaneously, mechanical performance is high, thermodynamics, chemical stability are high, and have high-adsorption-capacity and an adsorptive selectivity, can with heavy metal ion generation ion-exchange in the aqueous solution, reaching the purpose of heavy-metal ion removal, can be widely used in the fields such as catalysis, separation and absorption, is a kind of very potential sorbent material.
The present invention, by the grafting adsorption group, strengthens the composite modified of adsorbent, meets different adsorption conditionses to improve its adsorption efficiency, prepares to have cheaply high-adsorption-capacity and adsorptive selectivity and prepare simple porous aerogel adsorbent to be significant.
The invention provides and a kind ofly by sol-gal process and atmosphere pressure desiccation, prepare SiO
2/ TiO
2Aeroge is processed the new technology approach of high activity liquid waste: take butyl titanate, ethyl orthosilicate is raw material, and the formamide of take is controlled gel network structure as drying control chemical additive to improve pore passage structure, adopts sol-gel process to make SiO
2/ TiO
2Alcogel grafting adsorption group; Because the frame strength of plural gel is lower, easily cracking is broken, need to, in conjunction with post-processing steps such as low surface tension solvent replacement and constant pressure and dries, realize SiO
2/ TiO
2The atmosphere pressure desiccation preparation of aeroge; And using cerium as the simulation element of radionuclide, study the absorption property of compound porous aeroge to cerium, for the processing of high activity liquid waste provides a new technological approaches.
Although the processing nuke rubbish that geological disposal can be safer, the pre-concentration problem of the nuke rubbish of large volume are also one of research emphasis both domestic and external always.When adsorbent of the present invention is put wastewater treatment for height, adsorption capacity is large, it is convenient to reclaim, with low cost, easy to prepare, can meet efficient adsorption radioactive element under the prerequisite of different adsorption conditionses, reduce significantly the volume of high activity liquid waste, for the processing of high activity liquid waste provides a new technological approaches.
The accompanying drawing explanation
Fig. 1 is the flow chart of embodiment 1.
Fig. 2 is the SiO of embodiment 1 preparation
2/ TiO
2The aeroge scanning electron microscope (SEM) photograph
The specific embodiment
Below in conjunction with example, further illustrate the present invention, technical solution of the present invention is not limited to the following instantiation of lifting.
Embodiment 1
Press technological process shown in Figure 1:
(1) SiO
2The preparation of colloidal sol:
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.01moL/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then, add TEOS, at room temperature continue stirring and obtained even SiO in 30 minutes
2Colloidal sol.Ageing 24h, add expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：2g
TEOS：10mL
Aqueous hydrochloric acid solution: 30mL
PO：5mL。
(2) TiO
2The preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 200 rev/mins of strong agitation, solution B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol.By room temperature ageing 24h after this colloidal sol sealing.
Its raw material weight proportioning is as follows:
Butyl titanate 10mL
Absolute ethyl alcohol 40mL
Acetic acid 3mL
Redistilled water 5mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
Under vigorous stirring, by the above-mentioned SiO prepared
2Colloidal sol and TiO
2The full and uniform mixing of colloidal sol, and add the formamide of 1mL, obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel under 60 ℃, first by soaked in absolute ethyl alcohol, remove alcogel with displacement in unnecessary moisture content, then use the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.
SiO by preparation
2/ TiO
2The aeroge fragmentation, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h with the deionized water washing, is ground to 200 orders.Take through pretreated aeroge sample, be used as the adsorbent of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium.
Experiment concrete operation method: in the conical flask of 8 100mL, take respectively above-mentioned pretreated SiO
2/ TiO
2Aeroge, pipette 50mL ammonium ceric nitrate standard liquid in conical flask, and water-bath constant temperature oscillator (25 ℃) vibration is put in the sealed membrane sealing.(every 12 hours of early stage surveyed once constantly setting, every 24 hours of later stage surveyed once) take out a conical flask, pipette the centrifugation of 4mL dirty solution, pipette the 1mL supernatant in the 50mL volumetric flask, by deionized water, be diluted to scale, on ultraviolet/visible spectrophotometer, survey its absorbance, absorbance substitution calibration curve equation is drawn to the concentration of cerium, calculate SiO
2/ TiO
2Adsorbance, adsorption rate and the absorption ratio of aeroge to cerium in solution, result such as table 1.
Table 1
In solid-to-liquid ratio (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid) while being 3:500, equilibrium adsorption capacity 230mg/g, equilibrium adsorption rate 94%, equilibrium adsorption compares 12000mL/g.
Adopt sol-gel process by the synthetic SiO of phase-splitting approach
2/ TiO
2Porous gel has larger specific area and porosity, is to have contiguous network structure light wt porous material, cerium in solution is had to good absorption property, but time of equilibrium adsorption is longer, is about 140h; Initial concentration one regularly, changes the adsorbent consumption, SiO
2/ TiO
2Porous gel reduces gradually to the equilibrium adsorption capacity of cerium in solution; The equilibrium adsorption rate increases gradually, when solid-to-liquid ratio is 3:500, keeps stablizing constant; Equilibrium adsorption subtracts after than first, increasing, and when solid-to-liquid ratio is 3:500, maximum is arranged.
SiO by upper gained
2/ TiO
2Aeroge Sample Scan Electronic Speculum figure as shown in Figure 1, have larger specific area, porosity and good heat endurance, it is the light porous blocks of solid material with certain mechanical strength, cerium in solution is had to good absorption property, can be applicable to removal of heavy metal ions and nuclear waste disposal technique.
Embodiment 2
(1) SiO
2The preparation of colloidal sol:
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.01moL/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then, add TEOS, at room temperature continue stirring and obtained even SiO in 30 minutes
2Colloidal sol.Ageing 24h, add expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：3g
TEOS：20mL
Aqueous hydrochloric acid solution: 50mL
PO：10mL。
(2) TiO
2The preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 200 rev/mins of strong agitation, solution liquid B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol, ageing 24h, standby.Its raw material weight proportioning is as follows:
Butyl titanate 20mL
Absolute ethyl alcohol 70mL
Acetic acid 10mL
Redistilled water 8mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
Under vigorous stirring, by the above-mentioned SiO prepared
2Colloidal sol and TiO
2The full and uniform mixing of colloidal sol, and add 2mL formamide and 50ml
Solution, obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel under 60 ℃, first by soaked in absolute ethyl alcohol, remove alcogel with displacement in unnecessary moisture content then use the ethanolic solution (1:3 volume ratio) of ethyl orthosilicate and absolute ethyl alcohol to repeat above the operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.
By the sample fragmentation of preparation, with the deionized water washing, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h, be ground to 200 orders.Take the pretreated aeroge sample of a certain amount of process, be used as the adsorbent (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid is 6g/L waste water) of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium, testing process is with embodiment 1, result such as table 2.
Table 2
Under identical cerium concentration, by contrast and composite modified SiO
2/ TiO
2Porous aerogel, in the adsorption rate relation of identical adsorption time to cerium, can find, through the composite modified grafting of Nafion the SiO of sulfonic group
2/ TiO
2Aeroge has better adsorption rate to cerium, and adsorption time shortens greatly, has effectively improved adsorption efficiency.
Existing adsorption technology exists cost high, and preparation is complicated, or adsorption capacity is lower, without shortcomings such as adsorptive selectivities.SiO by upper gained
2/ TiO
2The aeroge sample is a kind ofly to have cheaply high-adsorption-capacity and adsorptive selectivity and prepare simple porous aerogel adsorbent, by the grafting sulfonic group as adsorption group, strengthen the composite modified of adsorbent, can meet different adsorption conditionses, greatly improved adsorption efficiency.
Composite modified SiO
2/ TiO
2Porous aerogel is about 90h to the time of equilibrium adsorption of cerium, and when initial, the rate of adsorption is very fast, passing in time, and the rate of adsorption slows down gradually, reaches balance to the 90h left and right, and final adsorption rate is up to 99.7%, and Ce elements is almost all absorbed; And there is no the SiO of modification
2/ TiO
2Porous aerogel is about 150h to the time of equilibrium adsorption of cerium, and the final adsorption rate of cerium is about to 82%.For from now on research work and engineering application provide theoretical foundation and practical basis, can offer reference for the processing of the nuclear waste of the military, civilian nuclear facilities production of other types simultaneously.
Embodiment 3
(1) SiO
2The preparation of colloidal sol:
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 001moL/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then, add TEOS, at room temperature continue stirring and obtained even SiO in 30 minutes
2Colloidal sol.Ageing 24h, add expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：1g
TEOS：10mL
Aqueous hydrochloric acid solution: 20mL
PO：4mL。
(2) TiO
2The preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 300 rev/mins of strong agitation, solution liquid B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol, ageing 28 hours, standby.Its raw material weight proportioning is as follows:
Butyl titanate 10mL
Absolute ethyl alcohol 40mL
Acetic acid 4mL
Redistilled water 4mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
Under vigorous stirring, by the above-mentioned SiO prepared
2Colloidal sol and TiO
2The full and uniform mixing of colloidal sol, and add 0.5mL formamide and 20ml nitrogen arsine III solution (0.005g.L
-1) (
CAS:1668-00-4), obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel is first removed moisture content unnecessary in alcogel by soaked in absolute ethyl alcohol with displacement and is then used the ethanolic solution of ethyl orthosilicate (1:3 volume ratio) and absolute ethyl alcohol to repeat above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in dry 72h left and right in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.Due to arsenazo with the arsenate chelation group, 4,6 valency elements are had higher selective, thereby reach the separation purpose.
By the sample fragmentation of preparation, with the deionized water washing, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h, be ground to 200 orders.Take the pretreated aeroge sample of a certain amount of process, be used as the adsorbent (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid is 6g/L waste water) of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium, testing process is with embodiment 1, result such as table 3.
Table 3
Under identical cerium concentration, composite modified SiO
2/ TiO
2Porous aerogel is about 72h to the time of equilibrium adsorption of cerium, and when initial, the rate of adsorption is very fast, passing in time, and the rate of adsorption slows down gradually, reaches balance to the 72h left and right, and final adsorption rate is up to 98%; And there is no the SiO of modification
2/ TiO
2Porous aerogel is about 150h to the time of equilibrium adsorption of cerium, and the final adsorption rate of cerium is about to 82%.By contrasting composite modified SiO
2/ TiO
2Porous aerogel can obtain in the adsorption rate relationship analysis of identical adsorption time to cerium, through the composite modified SiO of nitrogen arsine III
2/ TiO
2Aeroge has better adsorption rate to cerium, and adsorption time shortens greatly, has effectively improved adsorption efficiency.
Embodiment 4
(1) SiO
2The preparation of colloidal sol:
Under stirring condition, PEG is dissolved in the aqueous hydrochloric acid solution of 0.01moL/L, continue stirring and PEG was uniformly dissolved in 90 minutes, then, add TEOS, at room temperature continue stirring and obtained even SiO in 30 minutes
2Colloidal sol.Ageing 24h, add expoxy propane (PO), this colloidal sol good seal is placed in to 40 ℃ of baking ovens stand-by.Its raw material weight proportioning is as follows:
PEG：3g
TEOS：18mL
Aqueous hydrochloric acid solution: 25mL
PO：6mL。
(2) TiO
2The preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 250 rev/mins, solution B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol, ageing 20h, standby.Its raw material weight proportioning is as follows:
Butyl titanate 18mL
Absolute ethyl alcohol 60mL
Acetic acid 8mL
Redistilled water 10mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
Under vigorous stirring, by the above-mentioned SiO prepared
2Colloidal sol and TiO
2The full and uniform mixing of colloidal sol, and add 1.5mL formamide and the silica-based quaternized parting material of 20g, obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel carries out solvent exchange; After by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in 100 ℃ of baking ovens dry, can obtain SiO
2/ TiO
2The aeroge sample.
By the sample fragmentation of preparation, with the deionized water washing, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h, be ground to 200 orders.Take the pretreated aeroge sample of a certain amount of process, be used as the adsorbent (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid is 6g/L waste water) of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium, testing process is with embodiment 1, result such as table 4.
Table 4
| Adsorption rate (%)/adsorption time (h) | 24h | 48h | 72h | 120h | 150h |
| SiO 2/TiO 2Aeroge | 18% | 40% | 60% | 80% | 82% |
| Composite modified SiO 2/TiO 2Aeroge | 47% | 78% | 95% | 99.5% | 99.5% |
Under identical cerium concentration, composite modified SiO
2/ TiO
2Porous aerogel is about 72h to the time of equilibrium adsorption of cerium, and when initial, the rate of adsorption is very fast, passing in time, and the rate of adsorption is tending towards slowing down, and reaches balance to the 120h left and right, and final adsorption rate is up to 99.5%; And there is no the SiO of modification
2/ TiO
2Porous aerogel is about 150h to the time of equilibrium adsorption of cerium, and the final adsorption rate of cerium is about to 82%.By contrasting composite modified SiO
2/ TiO
2Porous aerogel can obtain in the adsorption rate relationship analysis of identical adsorption time to cerium, through the composite modified SiO of silica-based quaternized parting material
2/ TiO
2Aeroge has better adsorption rate to cerium, and has shortened adsorption time, has greatly improved adsorption efficiency.
Comparative Examples 1
SiO
2Colloidal sol and TiO
2Colloidal sol all adopts the gel method preparation, and does not carry out ageing, prepares adsorbent, then, be used to simulating the high wastewater treatment of putting, contrasts with embodiment 2, by comparing proof effect of the present invention.
(1) SiO
2The preparation of alcosol
Ethyl orthosilicate, absolute ethyl alcohol, deionized water are evenly mixed according to a certain volume, are 0.6 by nitric acid regulator solution pH value, and after hydrolysis 30min, the standing continuation hydrolysis of room temperature, make SiO under 353K
2Colloidal sol.
Ethyl orthosilicate 20mL
Absolute ethyl alcohol 30mL
Deionized water 5mL
(2) TiO
2The preparation of colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 200 rev/mins, solution B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol.Its raw material weight proportioning is as follows:
Butyl titanate 20mL
Absolute ethyl alcohol 50mL
Acetic acid 10mL
Redistilled water 10mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
Under vigorous stirring, by the above-mentioned SiO prepared
2Colloidal sol and TiO
2The full and uniform mixing of colloidal sol, and add 2mL formamide and 50mLNafion solution, obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel is first removed moisture content unnecessary in alcogel by soaked in absolute ethyl alcohol with displacement, then with ethanolic solution and the absolute ethyl alcohol of ethyl orthosilicate, repeats above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in drying in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.
By the sample fragmentation of preparation, with the deionized water washing, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h, be ground to 200 orders.Take the pretreated aeroge sample of a certain amount of process, be used as the adsorbent (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid is 6g/L waste water) of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium, testing process is with embodiment 1, result such as table 4.
Table 4
Comparative Examples 2
SiO
2Colloidal sol and TiO
2Colloidal sol all adopts the gel method preparation, and does not carry out ageing, does not also carry out the grafting processing and prepares adsorbent, with embodiment 2, contrasts, by comparing proof effect of the present invention.
(1) SiO
2The preparation of alcosol
Ethyl orthosilicate, absolute ethyl alcohol, deionized water are evenly mixed according to a certain volume, are 0.6 by nitric acid regulator solution pH value, and after hydrolysis 30min, the standing continuation hydrolysis of room temperature, make SiO under 353K
2Colloidal sol.
Ethyl orthosilicate 20mL
Absolute ethyl alcohol 30mL
Deionized water 5mL
(2) preparation of TiO2 colloidal sol:
Butyl titanate is mixed and obtains solution A with absolute ethyl alcohol; Acetic acid, redistilled water and equivalent absolute ethyl alcohol are mixed and obtain solution B.Under 200 rev/mins, solution B is dropwise added in solution A, the butyl titanate hydrolysis obtains TiO
2Colloidal sol.Its raw material weight proportioning is as follows:
Butyl titanate 20mL
Absolute ethyl alcohol 50mL
Acetic acid 10mL
Redistilled water 10mL.
(3) SiO
2/ TiO
2The preparation of aeroge:
By SiO
2Colloidal sol and TiO
2The colloidal sol full and uniform mixing of 1:1 by volume, and add the 2mL formamide, obtain SiO
2/ TiO
2Alcogel, by the SiO obtained
2/ TiO
2Alcogel is first removed moisture content unnecessary in alcogel by soaked in absolute ethyl alcohol with displacement, then with ethanolic solution and the absolute ethyl alcohol of ethyl orthosilicate, repeats above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel is placed directly in drying in 70 ℃ of baking ovens can obtain SiO
2/ TiO
2The aeroge sample.
By the sample fragmentation of preparation, with the deionized water washing, to neutral, then be placed in baking oven in 103 ℃ of oven dry 48h, be ground to 200 orders.Take the pretreated aeroge sample of a certain amount of process, be used as the adsorbent (mass volume ratio of adsorbent and ammonium ceric nitrate standard liquid is 6g/L waste water) of simulation ion Ce (IV) ion of Pu (IV), and adopt batch process research SiO
2/ TiO
2The absorption property of aeroge to cerium, testing process is with embodiment 1, result such as table 5.
Table 5
Comparative Examples 3
Tsing-Hua University in 1996 has carried out testing from the heat of removing Cs high activity liquid waste with Potassium titanium hexacyanoferrate, and flow used is 1.0mL/h, is equivalent to 2.27 bed volumes/h.Measure in efflux
137The activity of Cs is drawn the exchange curve.0.3g the Potassium titanium hexacyanoferrate exchanger is processed the 111.7mL high activity liquid waste,
37The penetrance of Cs is 44.4%.When the caesium penetrance was 0.1%, 41 bed volume feed liquids flow through pillar, and 1% penetrance occurs in 100 bed volume places, and by pillar, caesium only 44.4% penetrates when 253.6 bed volume feed liquids.
Claims (10)
1. a preparation method of putting the adsorbent of wastewater treatment for height, is characterized in that, comprises the steps:
(1) adopt split-phase method to prepare SiO
2Alcosol, adopt sol-gel process to prepare TiO
2Alcosol;
(2) by described TiO
2Alcosol and SiO
2Alcosol is ageing 20～28h respectively, then by the SiO after ageing
2Alcosol splashes into the TiO after ageing in proportion
2In alcosol, add formamide after mixing, reaction obtains SiO
2/ TiO
2Alcogel, to described SiO
2/ TiO
2Alcosol carries out post processing, and constant pressure and dry obtains composite modified SiO
2/ TiO
2Aeroge.
2. for height, put according to claim 1 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, when in step (2), adding formamide, add coating material.
3. for height, put according to claim 2 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, described coating material is
Solution, silica-based quaternized parting material, nitrogen arsine III or diethyl pentetic acid.
4. for height, put according to claim 1 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, described split-phase method prepares SiO
2The detailed process of alcosol is as follows:
Under stirring condition, polyethylene glycol is dissolved in aqueous hydrochloric acid solution, continue stirring polyethylene glycol is uniformly dissolved, in polyglycol solution, add ethyl orthosilicate, continue to stir the even SiO of acquisition
2Colloidal sol, add expoxy propane and get final product.
5. for height, put according to claim 4 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, the mass volume ratio of described polyethylene glycol, ethyl orthosilicate, aqueous hydrochloric acid solution and expoxy propane is: 1-3g:10-20mL:20-50mL:4-10mL.
6. for height, put according to claim 1 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, SiO described in step (2)
2Alcosol and TiO
2The silicon titanium mol ratio of alcosol is 1:1.
7. for height, put according to claim 1 the preparation method of the adsorbent of wastewater treatment, it is characterized in that, the last handling process described in step (2) is:
By SiO
2/ TiO
2Alcogel is first used soaked in absolute ethyl alcohol 20～25h under 55～65 ℃, after washing, again under 55～65 ℃, first use soaked in absolute ethyl alcohol 20～25h, then with ethanolic solution and the absolute ethyl alcohol of ethyl orthosilicate, repeats above operation; Finally by the SiO of immersion treatment
2/ TiO
2Alcogel dry 65～75h in 65～75 ℃ of baking ovens namely obtains SiO
2/ TiO
2Aeroge.
8. one kind high processing method of putting wastewater treatment, is characterized in that, comprises the steps:
(1) adopt split-phase method to prepare SiO
2Alcosol, adopt sol-gel process to prepare TiO
2Alcosol;
(2) by described TiO
2Alcosol and SiO
2Alcosol is ageing 20～28h respectively, then by the SiO after ageing
2Alcosol splashes into the TiO after ageing in proportion
2In alcosol, add formamide after mixing, reaction obtains SiO
2/ TiO
2Alcogel, to described SiO
2/ TiO
2Alcosol carries out post processing, and constant pressure and dry obtains composite modified SiO
2/ TiO
2Aeroge.
(3) by described composite modified SiO
2/ TiO
2Aeroge is added to height and puts in waste water, carries out adsorption treatment.
9. high processing method of putting wastewater treatment according to claim 8, is characterized in that, described adsorption time is 70～180h.
10. high processing method of putting wastewater treatment according to claim 8, is characterized in that, described adsorbent dosage is 2～10g/L waste water.
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| CN104043348A (en) * | 2014-06-25 | 2014-09-17 | 合肥学院 | Preparation method of hybrid membrane adsorbent for removing strontium ions in radioactive wastewater |
| CN105854744A (en) * | 2016-05-17 | 2016-08-17 | 浙江大学 | Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste |
| CN108371939A (en) * | 2018-05-08 | 2018-08-07 | 青岛翰兴知识产权运营管理有限公司 | A kind of porous spherical silica gel load nano-TiO2Heavy metal in waste water sorbing material preparation method |
| CN110479204A (en) * | 2019-08-13 | 2019-11-22 | 云南大学 | A kind of high adsorption TiO2The application of the preparation method and its absorbing heavy metal ions in water of aeroge |
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| CN104043348A (en) * | 2014-06-25 | 2014-09-17 | 合肥学院 | Preparation method of hybrid membrane adsorbent for removing strontium ions in radioactive wastewater |
| CN105854744A (en) * | 2016-05-17 | 2016-08-17 | 浙江大学 | Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste |
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| CN108371939A (en) * | 2018-05-08 | 2018-08-07 | 青岛翰兴知识产权运营管理有限公司 | A kind of porous spherical silica gel load nano-TiO2Heavy metal in waste water sorbing material preparation method |
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| CN111620561A (en) * | 2020-06-23 | 2020-09-04 | 中建材蚌埠玻璃工业设计研究院有限公司 | Method for preparing radioactive nuclear waste glass solidified body by microwave method |
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| CN112403439B (en) * | 2020-10-11 | 2022-09-02 | 兰州大学 | Uranium separation material and preparation method thereof |
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