CN108654558A - A kind of X-type zeolite and preparation method thereof being modified together with amidoxime, to the adsorption applications of ruthenium and caesium - Google Patents
A kind of X-type zeolite and preparation method thereof being modified together with amidoxime, to the adsorption applications of ruthenium and caesium Download PDFInfo
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- CN108654558A CN108654558A CN201810388067.5A CN201810388067A CN108654558A CN 108654558 A CN108654558 A CN 108654558A CN 201810388067 A CN201810388067 A CN 201810388067A CN 108654558 A CN108654558 A CN 108654558A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The present invention relates to a kind of preparation method together with amidoxime modified X-type zeolite, key step is as follows：Step 1 introduces amino：X-type zeolite is scattered in absolute ethyl alcohol, silane coupling agent hydro-thermal is added and is stirred at reflux；Step 2 introduces itrile group：Step 1 products therefrom is scattered in absolute ethyl alcohol, glutaraldehyde water solution is added and is stirred at room temperature, is scattered in absolute ethyl alcohol again after then washing is dry, adds iminodiacetonitrile, be then stirred at room temperature；Step 3 itrile group is converted into together with amidoxime group：Step 2 products therefrom is scattered in the aqueous solution of ethyl alcohol, is then added sodium carbonate and hydroxylamine hydrochloride, return stirring is dried after the washing of obtained solid product to get to the X-type zeolite being modified together with amidoxime.Preparation process of the present invention is simply controllable, reproducible, easy to operate, and the crystalline structure that the material of preparation has had has loaded on X-type zeolite together with amidoxime group, can effectively adsorb the Ru in water3+And Cs+, it is a kind of applicable sorbing material of ideal.
Description
Technical field
The present invention relates to a kind of together with X-type zeolite of amidoxime modification and preparation method thereof, to the adsorption applications of ruthenium and caesium, belongs to
Technical field of waste water processing.
Background technology
From on March 11st, 2011, nuclear leakage accident had occurred in Fukushima nuclear power station, causes a large amount of radionuclides and enters sea
Ocean, radioactive pollution cause the extensive concern of various circles of society.The radioactive pollutant for being discharged into ocean be all by U235, Pu239,
The fission product of Pu241, type probably have more than 40 kinds [4].When nuclear power station leaks, the radioactive nucleus that can be discharged into environment
Element mainly has131I、137Cs、134Cs、90Sr、58Co、60Co、110mAg、239Pu、54Mn、124Sb、65Zn、99mTc、241Am、95Zr and106Ru.There is the coastline up to 1.8 ten thousand kilometers in China, once nuclear power station leakage accident occurs, it is necessary to fast and effeciently supervise
Marine Radioactivity environmental aspect, timely early warning and forecast are surveyed, the crisis being likely to occur is taken precautions against and cope with.
P.G.M.Brown etc. thinks that state existing for the ruthenium of aftertreatment technology can be roughly divided into four classes：1) nitrosyl ruthenium
Nitrato complex；2) nitrosyl ruthenium nitrite complexes；3) ruthenium of noncoordinating cationic state, such as [RuNO (OH)]2+；
4)Ru4+With in the form of oxygen bridge existing for ruthenium [RuORu]4+。RuNO3+With NO3、NO2And H2The complex that the dentates such as O are formed can
It is summarized as following general formula：
[RuNO(NO3)X(H2O)5-x](3-x)+X=0~4
[RuNO(NO2)X(NO3)y(OH)3-x-y(H2O)5-x-y] x+y=0~4
It can be seen that RuNO3+With NO3、NO2And H2The dentates such as O formed complex both can with cation exist or
Can exist with anion, so to remove the Ru in nuclear leakage seawater3+、RuNO3+And its complex, it is necessary to can be to metal
Cation form reveals compatibility, also to there is the complex group of compatibility to metal complex anions.
Caesium is located at the Ith main group of period 6 in the periodic table of elements, belongs to alkali metal element, atomic number is 55, relatively
Atomic mass is 132.9, and color is golden yellow, and chemical valence is+1 valence.Chemical property of the caesium in alkali metal element is most active,
It is easily aoxidized in air, is existed in a salt form in nature, without elemental form, main compound is CsCl and carbonization
Caesium.Caesium is highly soluble in water.
The method of processing radionuclide mainly has：Chemical precipitation method, ion-exchange, membrane separation process, absorption method.Chemistry
The precipitation method are easy and fast to the radionuclide in water removal and heavy metal ion, but need that excessive precipitating reagent or mixed is added
Solidifying agent, these precipitating reagents and flocculant itself are toxic, and will produce a large amount of sludge, costly.Ion-exchange is as one
The ripe method of kind can be used for concentrating and absorb the radionuclide in water, but resin price is excessively high, and be easy by dirt
Dye, capability of resistance to radiation are weak.Membrane technology is at present still in the development phase, and technology is not very ripe, and film is easy to be polluted,
It is expensive.Absorption method is abundant with raw material sources, wide in variety, it is at low cost the advantages that, and adsorption rate is fast, adsorption capacity
Greatly, it is considered removing the most promising method of radionuclide.
Currently, common adsorbent includes mainly inorganic adsorbent, organic adsorbent, biological adsorption agent and composite material are inhaled
Attached dose.Although inorganic adsorbent has the characteristics that anti acid alkali performance, thermodynamic stability, chemical stability and radiation-resistant, its
Reaction rate is relatively low, and adsorption capacity is not high.Organic adsorbent surface typically contains a large amount of carboxyl, hydroxyl and alkoxy isoreactivity
Group, these groups can be combined with radionuclide, to which it is higher to the rate of adsorption and adsorption capacity of radionuclide,
But its radioresistance and thermodynamic stability be not high.Biological adsorption agent is since its cost is higher, complex operation and final
The problems such as disposition and be not widely used.Composite material adsorbent combines inorganic adsorbent and organic adsorbent two
The advantages of person is considered as a kind of most promising adsorbent.It is as compound together with amidoxime modified X-type zeolite prepared by the present invention
Material sorbent.
Invention content
The technical problem to be solved by the present invention is to be loaded on X-type zeolite together with amidoxime group, one kind is provided together with amidoxime
The preparation method of modified X-type zeolite, preparation process is simply controllable, reproducible, easy to operate, the crystalline substance that the material of preparation has had
Type structure has been loaded to together with amidoxime group on X-type zeolite, can effectively adsorb the Ru in water3+And Cs+, being a kind of ideal can apply
Sorbing material.
For the technical problem for solving proposed by the invention, the technical solution adopted by the present invention is：
A kind of preparation method together with amidoxime modified X-type zeolite, key step are as follows：
Step 1, X-type zeolite is prepared：Using tetraethyl ammonium hydroxide as presoma, deionized water is solvent, and sodium metasilicate is used as
Silicon source, sodium aluminate are used as silicon source, and it is Na to control molar ratio in the middle2O:Al2O3:SiO2:H2O=2.5~3.5:0.8~1.2:1.5
~2.5:190~210；First, tetraethyl ammonium hydroxide aqueous solution will be added in sodium silicate aqueous solution, is uniformly mixing to obtain mixing
Liquid；Then sodium aluminate solution is added in above-mentioned mixed liquor, is stirred evenly, 12~20h of hydrothermal crystallizing at 95~105 DEG C, institute
Product is washed, dry to get to X-type zeolite；
Step 2, the X-type zeolite being modified together with amidoxime is prepared
2-1 introduces amino：X-type zeolite is scattered in absolute ethyl alcohol, silane coupling agent (APTES) water at 80 DEG C is added
Thermal agitation reflux 16h, amino is introduced into X-type zeolite, spare after washing is dry；Wherein, the matter of X-type zeolite and silane coupling agent
Amount is than being 4.5~5.5:1；
2-2 introduces itrile group：Step 2-1 products therefroms are scattered in absolute ethyl alcohol, glutaraldehyde water solution is added in room temperature
The volume ratio of lower stirring 3h, glutaraldehyde water solution and absolute ethyl alcohol is 100:1, it is scattered in anhydrous second again after then washing is dry
In alcohol, iminodiacetonitrile (IDAN), the IDAN added and step 2-1 products therefroms mass ratio 0.8~1.2 are added:1, with
After be stirred at room temperature 3~6h, it is spare after washing is dry；
2-3 itrile groups are converted into together with amidoxime group：Step 2-2 products therefroms are scattered in the aqueous solution of ethyl alcohol, are then added
Enter sodium carbonate and hydroxylamine hydrochloride, the mass ratio of 2-2 products and sodium carbonate, hydroxylamine hydrochloride is 1:0.8~1.2:0.8~1.2.In temperature
Condensing reflux stirs 2~8h at 50~90 DEG C of degree, dries after the washing of obtained solid product and is boiled to get to the X-type being modified together with amidoxime
Stone.
By said program, in step 1, the concentration range of sodium silicate aqueous solution is between 1.24~1.26mol/L, tetraethyl
The concentration range of ammonium hydroxide aqueous solution between 0.10~0.14mol/L, the concentration range of sodium aluminate aqueous solution 1.19~
Between 1.21mol/L.
By said program, a concentration of the 12~15% of glutaraldehyde water solution in step 2-2.
By said program, the volume ratio of second alcohol and water is 4~5 in the aqueous solution of ethyl alcohol in step 2-3：1.
By said program, it is most preferably 1 that sodium carbonate and hydroxylamine hydrochloride, which add the ratio of quality,:1.
The synthetic route of the X-type zeolite of the present invention being modified together with amidoxime is as follows：
Compared with prior art, the beneficial effects of the invention are as follows：
First, the invention firstly uses hydrothermal crystallization methods to prepare X-type zeolite, negative followed by silane coupling agent (APTES)
It carries on amino to X-type zeolite, then the itrile group in diamino dintrile (IDAN) is loaded on X-type zeolite, finally utilizes hydrochloric acid
Azanol converts nitrile group in the X-type zeolite for obtaining being modified together with amidoxime group together with amidoxime.Its mechanism of action as adsorbent
It is that X-type zeolite provides big specific surface area and duct, is convenient for Ru3+And Cs+Into absorbent interior, by what is formed together with amidoxime group
With ruthenium and caesium chemisorption occurs for active site, has the function that efficiently to administer containing ruthenium and caesium waste water.
Second, it is raw material that the present invention, which directly utilizes sodium metasilicate and sodium aluminate, obtains the X-type zeolite of high-purity；And with tetrem
Base ammonium hydroxide is that template prepares X-type zeolite, has comparable flexibility, experimental implementation is simple, and X-type zeolite can be prevented mutual
The case where reunion.
Third, the X-type zeolite of the present invention being modified together with amidoxime is as adsorbent, and removal effect is high, and adsorption time is short,
Initial concentration is in the simulation ruthenium waste water of 12.4ppm, and adsorption equilibrium can reach in 30min, to the removal effect of ruthenium and caesium
99% or more can be reached；Also, it can be detached well with water, natural subsidence 1h can be settled completely, handle waste water
Water quality afterwards is limpid, and adsorbent and ruthenium heavy metal precipitation get off, and carries out mud-water separation, not will produce secondary pollution matter and enter water
Body
4th, in the X-type zeolite whole preparation process being modified together with amidoxime, temperature controls always 100 the present invention
DEG C hereinafter, experimental implementation safety is higher.
Description of the drawings
Fig. 1 is the SEM characterizations of 1 gained X-type zeolite of embodiment.
Fig. 2 is that the XPS characterization collection of illustrative plates of X-type zeolite, Fig. 2 a are XPS measuring spectrum to embodiment 1 afterwards before modified, and Fig. 2 b are XPS-
C 1s spectrograms, Fig. 2 c are XPS-N 1s spectrograms, and Fig. 2 d are XPS-O 1s spectrograms.
Fig. 3-1 is the relational graph for adsorbing ruthenium and pH in embodiment 3 together with the X-type zeolite that amidoxime is modified.
Fig. 3-2 is the relational graph for adsorbing caesium and pH in embodiment 3 together with the X-type zeolite that amidoxime is modified.
Fig. 4 is the relational graph for adsorbing ruthenium and interfering ion in embodiment 4 together with the X-type zeolite that amidoxime is modified.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Embodiment 1
A kind of preparation method for the X-type zeolite being modified together with amidoxime, it is prepared in accordance with the following steps：
The preparation of 1.X type zeolites
Using tetraethyl ammonium hydroxide as presoma, deionized water is solvent, and sodium metasilicate is used as silicon source, and sodium aluminate is used as aluminium
Source.Molar ratio is tetraethyl ammonium hydroxide in the middle:Deionized water:Sodium metasilicate:Sodium metaaluminate=0.05:2100:1:1.X-type zeolite
Building-up process it is as follows：
17.052g sodium metasilicate is dissolved in 48ml deionized waters, is mixed evenly to obtain sodium silicate solution, 4.918g sodium metaaluminates
It is dissolved in 50ml deionized waters, is mixed evenly to obtain sodium aluminate solution；It is added 28ml 0.12mol/L's into sodium silicate solution
Tetraethyl ammonium hydroxide solution, stirs evenly, and then sodium aluminate solution is added in above-mentioned mixed liquor, stirs evenly, ultrasound, so
The stainless steel autoclave with polytetrafluoroethyllining lining of 100ml is poured into afterwards, and the hydrothermal crystallizing 16h at 100 DEG C then takes out
Autoclave is cooled to room temperature；Products therefrom is washed with deionized water repeatedly, is boiled to get to X-type within dry 24 hours at 40 DEG C
Stone.
2. together with the preparation for the X-type zeolite that amidoxime is modified, including introducing amino, introducing itrile group, itrile group and being converted into together with oxamidino
Three steps of group, it is specific as follows：
1) amino is introduced：Amino is introduced into X-type zeolite using silane coupling agent (APTES).1g X-type zeolites are taken to disperse
In 100ml absolute ethyl alcohols, 0.2g APTES are added, hydro-thermal is stirred at reflux 16h at 80 DEG C, subsequent sample deionized water and
Absolute ethyl alcohol is alternately washed 3 times, and product is placed in 60 DEG C of vacuum drying chamber drying 12h；
2) itrile group is introduced：Using glutaraldehyde as cross linker, IDAN is grafted onto on X-type zeolite.By the product of 1g steps 1)
It is dissolved in 200ml absolute ethyl alcohols, the glutaraldehyde solution of 2ml is added, stirs 3h at ambient temperature, then wash, vacuum drying
12h, product are scattered in 200ml absolute ethyl alcohols, and the IDAN of 1.5g is added, and 3h, products therefrom deionization is stirred at room temperature
Water and ethyl alcohol alternately washing 3 times, product is placed at 60 DEG C and is dried in vacuo 12h；
3) itrile group is converted into together with amidoxime group：Product in step 2) is scattered in 90% (ethyl alcohol of 200ml：Water) solution
In, the sodium carbonate and 1.0g hydroxylamine hydrochlorides of 1.0g are added into solution, in the case where temperature is 70 DEG C, condensing reflux stirs 3h, will produce
Alternately washing 3 times of object deionized water and ethyl alcohol are placed at 60 DEG C and are dried in vacuo to get to the X-type zeolite being modified together with amidoxime.
The scanning electron microscope for the X-type zeolite that the present invention is prepared is as shown in Figure 1, it is observed that clearly from two width figures
Regular octahedron structure can be concluded that X-type zeolite has synthesized according to the structure feature of X-type zeolite.
The XPS characterizations of X-type zeolite from XPS survey spectrum (figure a) as shown in Fig. 2, it can be seen that, change after before modified
X-type zeolite after property, produces a new peak N1s at 399eV combination energy, this is because the modified addition for having amino,
N element content is caused to increase, intensity increases at N1s；Also, the peaks O1s that the modified combination positioned at 532eV can be located, intensity
There is certain decrease, is located at 284.8eV and the peaks C1s that can locate, intensity is combined to have certain enhancing, this is because it is modified, together with
Amidoxime group loads on X-type zeolite, and C element content is caused to increase, and C1s intensity is enhanced.
It is observed that after before modified from XPS C1s spectrum (figure b), it is located at 284.6eV, 285.2eV and 286.4eV
There is certain variation in conjunction with the peak that can locate.Wherein 284.6eV, 285.2eV and 286.4eV combine the peak that can locate respectively represent C-C,
C-N and C-O keys.Since amino loads on X-type zeolite, C-NH2Content increases, and causes to be located at the C-N that 285.2eV combinations can be located
Peak intensity enhances.
It is observed that modified X-type zeolite is compared to X-type zeolite, adsorption peak from XPS N1s spectrum (figure c)
There is apparent variation, combines the peak that can locate to respectively represent N ≡ C-CH and H positioned at 399.4eV and 400.2eV2N-C=NOH (ammonia
Oximido group), due to itrile group introducing and together with the conversion of amidoxime group, N ≡ C-CH and H2The content of N-C=NOH increases, and causes
99.4eV and 400.2eV combinations can enhance.This result, which is again demonstrated, have been loaded to together with amidoxime group on X-type zeolite.It is located at
401.5eV combines the peak of energy to represent N+。
It is observed that combining the peak that can locate positioned at 531eV, 532.4eV and 533eV from XPS O1s spectrum (figure-d)
Changed afterwards before modified.It being carried out together with oximes reaction using hydroxylamine hydrochloride, oxygen-containing functional group has certain reduction, but
It is due to so that N-O keys generate, causing N-O linkage contents to increase so that 532.4eV combines the peak intensity that can locate to enhance together with oximes.
Embodiment 2
Together with amidoxime be modified X-type zeolite to Ru in water3+Removal
Using 50ml centrifuge tubes as reaction vessel, by a concentration of 10mg/L of 20ml, the simulation ruthenium waste water that pH is 3 pours into centrifuge tube
In, the X-type zeolite being modified together with amidoxime prepared by the embodiment 1 of 0.1g/L is added, it can in 30min to the removal rate of ruthenium and caesium
To reach 99% or more.
Embodiment 3
Under different pH influence conditions, the X-type zeolite being modified together with amidoxime is to the removal rate of ruthenium, caesium.
Using 50ml centrifuge tubes as reaction vessel, reaction volume 20ml, the embodiment 1 that 0.2g/L is added into centrifuge tube is made
The standby X-type zeolite being modified together with amidoxime.Simulation ruthenium waste water initial concentration be 12.4mg/L, adjust simulation Ru waste water pH=1,2,
3,4,5,6；Simulation caesium waste water initial concentration is 10.0mg/L, the pH=2 of simulation caesium waste water, 4,5,6,7,8,9,10, is added respectively
Enter into centrifuge tube, is respectively 25 DEG C, isothermal vibration 30min in temperature, studies influences of the different pH to absorption.
By when pH is less than 3, the X-type zeolite being modified together with amidoxime is to Ru known to Fig. 3-13+Removal rate with pH increase
And increase, pH be more than 3 when, together with amidoxime be modified X-type zeolite to Ru3+Removal rate have apparent decline.Its reason H
+ can be with [Ru (NO) (H in solution2O)5]3+Competitive Adsorption is formed, pH is smaller, the H in solution+It is more, Ru3+Removal rate is lower；
When pH is more than 3, due to foring Ru (NO) (OH) in solution3Colloid, to hinder adsorbent to Ru3+Absorption, make
Obtain Ru3+Removal rate decline, therefore determine that the pH of best absorption Ru is 3, and pH is set as 3 in subsequent experimental.
By Fig. 3-2 it is found that pH be less than 3 when, together with amidoxime be modified X-type zeolite to Cs+Removal rate it is not high, this is because
H+And Cs+Competitive Adsorption is formd, when pH is more than 4, adsorbent is to Cs+Removal rate stablize in 90% or so, pH to absorption
It influences less, from resource to consider, it is optimal adsorption pH to set pH as 7.
Embodiment 4
Under disturbance ion and concentration conditions, removal rate of the modified X-type zeolite to ruthenium.
Using 50ml centrifuge tubes as reaction vessel, reaction volume 20ml adds 1 preparation of 0.1g/L embodiments into centrifuge tube
Together with amidoxime be modified X-type zeolite, simulation ruthenium waste water initial concentration be 12.4mg/L, adjust simulation Ru waste water pH=3 addition
Into centrifuge tube, then to being separately added into various concentration (0.005,0.01,0.02,0.05,0.1mol/L) in centrifuge tube
NaCl, KCl, CaCl2, it is 25 DEG C, isothermal vibration 30min in temperature, to study the influence of disturbance ion pair absorption.
The results are shown in Figure 4, it is known that, 3 kinds of interfering ions are to Ru3+Adsorbance interference effect size order be：Ca2+＞ K+
＞ Na+, this is because foreign ion can enter in absorption duct, physical absorption, competitive Adsorption site are formed in absorbent interior
Caused by, Ca2+Influence to absorption is in 50% or more, K+Influence to absorption is in 10% or so, Na+Influence to absorption exists
5% or so；Because of Ca2+Chelate can be formed with amino so that competitive Adsorption is stronger, to being inhaled together with amidoxime modified X-type zeolite
Attached Ru3+Influence bigger.
Embodiment 5
Embodiment 5 difference from example 1 is that：IDAN is added in the preparation for the X-type zeolite being modified together with amidoxime
Amount is 1.0g/g (X-type zeolite), and the dosage of hydroxylamine hydrochloride and sodium carbonate is 0.5g/g (X-type zeolite)；Itrile group is converted into together with ammonia
The temperature of oximido group is 80 DEG C, reaction time 4h.Other reaction conditions are consistent with embodiment 1.
Embodiment 6
Embodiment 6 difference from example 1 is that：IDAN is added in the preparation for the X-type zeolite being modified together with amidoxime
Amount is 2.0g/g (X-type zeolite), and the dosage of hydroxylamine hydrochloride and sodium carbonate is 1.5g/g (X-type zeolite), and last itrile group is converted into
Temperature together with amidoxime group is 60 DEG C, reaction time 5h.Other reaction conditions are consistent with embodiment 1.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of preparation method together with amidoxime modified X-type zeolite, it is characterised in that key step is as follows：
Step 1 introduces amino：X-type zeolite is scattered in absolute ethyl alcohol, silane coupling agent hydro-thermal at 70 ~ 90 DEG C is added and stirs
Flow back 14 ~ 18 h, and amino is introduced into X-type zeolite, spare after washing is dry；
Step 2 introduces itrile group：Step 1 products therefrom is scattered in absolute ethyl alcohol, glutaraldehyde water solution is added and stirs at room temperature
2 ~ 4h is mixed, is scattered in absolute ethyl alcohol again after then washing is dry, is added iminodiacetonitrile, be then stirred at room temperature
3 ~ 6h, it is spare after washing is dry；
Step 3 itrile group is converted into together with amidoxime group：Step 2 products therefrom is scattered in the aqueous solution of ethyl alcohol, carbon is then added
Sour sodium and hydroxylamine hydrochloride, condensing reflux stirs 2 ~ 8h at 50 ~ 90 DEG C of temperature, dried after the washing of obtained solid product to get to
The X-type zeolite being modified together with amidoxime.
2. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that the X-type boiling
The preparation method of stone is as follows：Using tetraethyl ammonium hydroxide as presoma, deionized water is solvent, and sodium metasilicate is used as silicon source, aluminic acid
Sodium is used as silicon source, and it is Na to control molar ratio in the middle2O:Al2O3:SiO2:H2O=2.5~3.5:0.8~1.2:1.5~2.5:190~210；
First, tetraethyl ammonium hydroxide aqueous solution will be added in sodium silicate aqueous solution, is uniformly mixing to obtain mixed liquor；Then by sodium aluminate
Solution is added in above-mentioned mixed liquor, stirs evenly, 12 ~ 20h of hydrothermal crystallizing at 95 ~ 105 DEG C, and products therefrom is washed, dry,
Obtain X-type zeolite.
3. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 2, it is characterised in that sodium metasilicate is water-soluble
The concentration range of liquid between 1.24 ~ 1.26mol/L, the concentration range of tetraethyl ammonium hydroxide aqueous solution 0.10 ~
Between 0.14mol/L, the concentration range of sodium aluminate aqueous solution is between 1.19 ~ 1.21mol/L.
4. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that X-type in step 1
The mass ratio of zeolite and silane coupling agent is 4.5 ~ 5.5:1.
5. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that penta in step 2
The volume ratio of a concentration of the 12 ~ 15% of dialdehyde aqueous solution, glutaraldehyde water solution and absolute ethyl alcohol is 100:0.5~1.5.
6. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that thrown in step 2
Iminodiacetonitrile and step 1 the products therefrom mass ratio 0.8 ~ 1.2 added:1.
7. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that second in step 3
The volume ratio of second alcohol and water is 4 ~ 5 in the aqueous solution of alcohol：1.
8. a kind of preparation method together with amidoxime modified X-type zeolite according to claim 1, it is characterised in that step 2 product
Mass ratio with sodium carbonate, hydroxylamine hydrochloride is 1:0.8~1.2:0.8~1.2.
9. claim 1 the method prepare together with amidoxime modified X-type zeolite.
10. described in claim 9 together with amidoxime modified X-type zeolite to the adsorption applications of ruthenium and caesium.
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| CN201810388067.5A Pending CN108654558A (en) | 2018-04-26 | 2018-04-26 | A kind of X-type zeolite and preparation method thereof being modified together with amidoxime, to the adsorption applications of ruthenium and caesium |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990011826A1 (en) * | 1989-03-31 | 1990-10-18 | LAGSTRÖM, Göran | Uranium adsorbent |
| CN103223333A (en) * | 2013-04-15 | 2013-07-31 | 河海大学 | Di-amidoxime group containing modified silica gel adsorbent and preparation method thereof |
-
2018
- 2018-04-26 CN CN201810388067.5A patent/CN108654558A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990011826A1 (en) * | 1989-03-31 | 1990-10-18 | LAGSTRÖM, Göran | Uranium adsorbent |
| CN103223333A (en) * | 2013-04-15 | 2013-07-31 | 河海大学 | Di-amidoxime group containing modified silica gel adsorbent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 谭美易: "磁性X型沸石的制备及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 赵英国: "偕胺肟基纳米材料的合成及其对铀的吸附性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
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