CN107311195A - A kind of preparation method and application of magnetic 5A molecular sieves - Google Patents
A kind of preparation method and application of magnetic 5A molecular sieves Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses a kind of method for preparing magnetic 5A molecular sieves and application, this method is：By FeCl2·4H2O and FeCl3·6H2O is added to the water, and NH is added after ultrasonic agitation heating3·H2O, obtains solidliquid mixture, then carries out magnetic absorption, washing and drying process, obtains magnetic Fe3O4；Using sodium aluminate as silicon source, sodium metasilicate is silicon source, and sodium hydroxide is alkali source, and water is solvent, adds calcium chloride, citric acid and above-mentioned magnetic Fe3O4, magnetic 5A molecular sieves are prepared in ultrasound field.The present invention prepares magnetic 5A molecular sieves, the magnetic molecule sifter device has the advantages that specific surface area is high, absorption property is strong, easily separated by externally-applied magnetic field with reaction solution using ultrasonic Wave heating by adding auxiliary agent.Ultrasonic wave and outer adding assistant are acted synergistically on preparation magnetic 5A molecular sieves by the present invention, can improve chemical reaction velocity, energy-conserving and environment-protective, and make the magnetic 5A molecular sieve uniform particle sizes of preparation, pattern rule.
Description
Technical field
The invention belongs to 5A technical field of molecular sieve preparation, and in particular to a kind of preparation method of magnetic 5A molecular sieves and should
With.
Background technology
5A molecular sieves have excellent adsorptivity, ion exchangeable and catalytic, and they are also to play in petrochemical industry
Very important effect, the effective aperture of 5A molecular sieves is 0.51 nanometer, and the cut off diameter of n-alkane molecule is about 0.49 to receive
Rice, and isoparaffin, cycloalkane and aromatic hydrocarbon is all more than 0.55 nanometer, and because the effective aperture of just 5A molecular sieves is
Between the cut off diameter of n-alkane molecule and non-n-alkane molecule their diameter, so only n-alkane can
Into the duct of 5A molecular sieves, so as to which n-alkane is separated from mixture.Appendix is a certain amount of in molecular sieve
Magnetic particle, i.e., using magnetic separation technique, by it, the quick separating from suspension is reclaimed.At present, the research collection of magnetic molecule sieve
In it is standby and characterize in magnetic molecule sieve series.In terms of current research present situation, the preparation of magnetic 5A molecular sieves and heavy metal ion are handed over
Change absorption property and Magneto separate recovering effect is also rarely reported.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of magnetic 5A points for above-mentioned the deficiencies in the prior art
The preparation method and application of son sieve.The present invention joins together the load of ultrasound, auxiliary agent and magnetic to prepare magnetic 5A molecular sieves, can
To improve chemical reaction velocity, energy-conserving and environment-protective, and make the magnetic 5A molecular sieve uniform particle sizes of preparation, pattern rule, to preparation
Magnetic molecule sieve provides new approach, new thinking, while the purpose of low-carbon environment-friendly has also been reached, before wide development
Scape.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of preparation method of magnetic 5A molecular sieves, comprises the following steps：
1) by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, under protective atmosphere, is carried out in ultrasonic wave anti-
Should, while being warming up to 75 DEG C~85 DEG C, NH is added after constant temperature3·H2O, continues fully reaction and obtains solidliquid mixture, solid-liquid is mixed
After compound natural cooling, the magnetisable material in solidliquid mixture is adsorbed using magnet, washed, magnetic is obtained after drying
Fe3O4；
2) sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution A；
Sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, solution B is obtained；Then in ultrasonic wave
Under conditions of vibration, solution B is added drop-wise in solution A, continues supersonic oscillations after completion of dropping, gel is obtained；In solution A partially
The mass ratio of sodium metasilicate is (1.34~1.39) in sodium aluminate and solution B: 1；
3) citric acid, calcium chloride and magnetic Fe are added to gel3O4, Al in citric acid and gel2O3Mol ratio be 0.65
~0.85, calcium chloride is 90~100g/L, Fe with gel solid-to-liquid ratio3O4Addition be solid material quality 10%~15%；
The crystallization under conditions of supersonic oscillations, temperature is 75 DEG C~95 DEG C, reaction terminates rear natural cooling and filtered, and washing is extremely
The pH value of product is 9~10, then dries, obtains magnetic 5A molecular sieves.
Step 1) in：The addition of raw material is：Every liter of distilled water adds (18.75~31.25) g FeCl2·4H2O、
(56.25~68.75) g FeCl3·6H2O, every liter of distilled water adds 125mL NH3·H2O。
In step 1), the power of ultrasonic response is 100W, adds NH3·H2Continue to react 20min~40min after O.
In step 1), drying temperature is 65 DEG C~75 DEG C, and the time is 5h~6h.5th, one kind according to claim 1
The preparation method of magnetic 5A molecular sieves, it is characterised in that the concentration of sodium metaaluminate is 96g/L~100g/L, hydrogen in the solution A
The concentration of sodium oxide molybdena is 20g/L~28g/L；In the solution B concentration of sodium metasilicate be 72g/L~76g/L, sodium hydroxide it is dense
Spend for 20g/L~28g/L.
Step 2) in, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasonic wave after completion of dropping
Vibrate 40min~60min.
Step 3) in, crystallization time is 2h~6h.
Step 3) in, using distillation water washing, then in 110 DEG C of dry 5h~6h.
Application of the magnetic 5A molecular sieves in absorption heavy metal ions in wastewater.Specifically for Adsorbing Lead Ion in Polluted Water.
The present invention has advantages below compared with prior art：
The preparation method of the magnetic 5A molecular sieves of the present invention, passes through FeCl2·4H2O and FeCl3·6H2O is added to the water, and surpasses
Sound stirring obtains magnetic Fe3O4；Using sodium aluminate as silicon source, sodium metasilicate is silicon source, and sodium hydroxide is alkali source, and water is solvent, ultrasonic wave
Vibration, obtains gel；Add calcium chloride, citric acid and magnetic Fe3O4, magnetic 5A molecular sieves are prepared in ultrasound field.This hair
It is bright to use chemical reagent for raw material, outer adding assistant citric acid is added, magnetic 5A molecules are prepared under ultrasonic activation heat effect
Sieve, the magnetic molecule sifter device has the advantages that specific surface area is high, absorption property is strong, easily separated by externally-applied magnetic field with reaction solution.
Ultrasonic wave and outer adding assistant are acted synergistically on preparation magnetic 5A molecular sieves by the present invention, can improve chemical reaction velocity, are saved
Environmental protection, and make the magnetic 5A molecular sieve uniform particle sizes of preparation, pattern rule.
Experiment shows：The present invention can effectively solve the problem that the difficult separation problem of in molecular sieve application and reaction solution.By Adsorption of Lead
Ion is tested, and the adsorption rate of magnetic molecule sieve is both greater than more than 93%, and is easy to using externally-applied magnetic field to separate with reaction solution,
Application of the magnetic molecule sieve in absorption industry will be greatly promoted.The crystallinity of magnetic 5A molecular sieve products prepared by the present invention
Height, crystal distribution is well-balanced, and even particle size, complete crystal form, crystal morphology is regular, in the cube shaped of rule.Present invention system
Standby magnetic 5A molecular sieves have specific surface area high, and absorption property is strong, the advantages of easily being separated by externally-applied magnetic field with reaction solution.
The load of ultrasound, auxiliary agent and magnetic is joined together to prepare magnetic 5A molecular sieves, new way is provided to magnetic molecule sieve is prepared
Footpath, new thinking, while the purpose of low-carbon environment-friendly has also been reached, with vast potential for future development.
Further, magnetic 5A molecular sieves of the invention use chemical reagent for raw material, add citric acid, are made in ultrasonic wave
A kind of standby magnetic 5A molecular sieves, it is proposed that new technology for preparing magnetic 5A molecular sieves.
Further, preparation and the application cost of magnetic 5A molecular sieves greatly reduces in the present invention.Adopted in preparation process
With outer adding assistant citric acid, and ultrasonic activation heating is added, the reaction time is substantially reduced, crystallization temperature is reduced, saved
Energy consumption；Magneto separate is utilized simultaneously, the utilization rate of molecular sieve is improved, with very strong commercial competitiveness, me can be promoted energetically
The fast development of state's molecular sieve.
Brief description of the drawings
Fig. 1 is the XRD of magnetic 5A molecular sieves prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM pictures of magnetic 5A molecular sieves prepared by the embodiment of the present invention 1；
Fig. 3 is the x-ray photoelectron spectroscopy figure of magnetic 5A molecular sieves prepared by the embodiment of the present invention 1；
Fig. 4 is the infrared spectrum of magnetic 5A molecular sieves prepared by the embodiment of the present invention 2.
Embodiment
A kind of method for preparing magnetic 5A molecular sieves of the present invention, it is characterised in that this method comprises the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, every liter of distilled water add (18.75~
31.25)g FeCl2·4H2O, (56.25~68.75) g FeCl3·6H2O；Under nitrogen protective condition in ultrasonic wave (100W)
Reacted, while being warming up to 75 DEG C~85 DEG C, NH is added after constant temperature3·H2O, every liter of distilled water adds 125mL NH3·H2O；
Continue to obtain solidliquid mixture after reacting 20min~40min, after after the solidliquid mixture natural cooling, using magnet to solid
Magnetisable material in liquid mixture is adsorbed, and then carries out cyclic washing to the magnetisable material that absorption is obtained, and is 65 in temperature
DEG C~75 DEG C under conditions of dry 5h~6h after, obtain magnetic Fe3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min~60min, obtains gel；The concentration of sodium metaaluminate is 96g/L~100g/L, sodium hydroxide in the solution A
Concentration be 20g/L~28g/L, the concentration of sodium metasilicate is 72g/L~76g/L in the solution B, and the concentration of sodium hydroxide is
20g/L~28g/L；The mass ratio of sodium metasilicate is (1.34~1.39) in sodium metaaluminate and solution B in the solution A: 1；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, citric acid, calcium chloride and magnetic are then added
Property Fe3O4, Al in citric acid and gel2O3Mol ratio be 0.65~0.85, calcium chloride and gel solid-to-liquid ratio are 90~100g/
L, Fe3O4Addition be solid material quality 10%~15%；In supersonic oscillations, temperature is 75 DEG C~95 DEG C of condition
Filtered after lower crystallization 2h~6h, natural cooling, it is 9~10 to adopt and be washed with distilled water to the pH value of product, be then 110 in temperature
5h~6h is dried under conditions of DEG C, magnetic 5A molecular sieves are obtained.
Technical scheme is described in further detail below by drawings and examples.
Embodiment 1
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl2·4H2O、FeCl3·6H2O
It is the corresponding addition 25gFeCl of every liter of distilled water with the addition of distilled water2·4H2O, adds 62.5g FeCl3·6H2O；Nitrogen
Reacted under protective condition in ultrasonic wave, while being warming up to 75 DEG C, NH is added after constant temperature3·H2(every liter of distilled water is added O
125mLNH3·H2O)；Continue to obtain solidliquid mixture after reacting 20min, after after the solidliquid mixture natural cooling, utilize magnetic
Iron is adsorbed to the magnetisable material in solidliquid mixture, then cyclic washing is carried out to the magnetisable material that absorption is obtained, in temperature
Spend to be dried under conditions of 65 DEG C after 5h, obtain magnetic Fe3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.34: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
The calcium chloride for being 90g/L for 0.65 citric acid, solid-to-liquid ratio, 10% magnetic Fe for accounting for solid material quality3O4, in ultrasonic wave
Vibration, temperature is crystallization 4h under conditions of 75 DEG C, is filtered after natural cooling, adopt be washed with distilled water to the pH value of product for 9~
10,5h then is dried under conditions of temperature is 110 DEG C, magnetic 5A molecular sieves are obtained.
XRD, SEM, XPS and FTIR are carried out to magnetic 5A molecular sieves manufactured in the present embodiment to characterize, as a result such as Fig. 1 to Fig. 3.
Fig. 1 is the XRD of magnetic 5A molecular sieves prepared by embodiment 1, it can be seen that magnetic 5A types manufactured in the present embodiment point
The data of son sieve X ray diffracting data and standard diagram are basically identical (JCPDF-39-0222), i.e., be respectively 7.16 in 2 θ,
10.12,12.40,16.06,21.64,23.96,27.10,29.92,34.16 nearby have the strong peak of diffraction to occur.From whole XRD
From the point of view of, diffraction maximum is sharp and intensity is big, and explanation adds the method effect that citric acid prepares magnetic 5A type molecular sieves with ultrasonic method
Very well.
Fig. 2 is the SEM photograph of magnetic 5A molecular sieves manufactured in the present embodiment, and the crystallinity of product is high, and crystallization degree is preferable,
Particle diameter is more uniform, and the cube shaped of rule is presented.Fig. 3 is the x-ray photoelectron spectroscopy of magnetic 5A molecular sieves, shows in figure readability of spectral line
Si is shown2p、A12p、OlsAnd NalsDeng peak, show that magnetic molecule sieve surface has the elements such as Si, Al, O and Na, spectral line have also appeared
Faint Fe2pPeak, show surface with the presence of Fe elements, be computed understand magnetic molecule sieve surface Fe3O4The quality that content is
Fraction is 2.79%, with reference to chemical analysis above, illustrates unstable with the iron of isomorphous substitution into molecular sieve, high temperature reduction bar
Substantially Fe is all generated under part3O4, the magnetic molecule sieve prepared under the method, the Fe generated are also indicated that in addition3O4With formation
Molecular sieve is present with hybrid form.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 93.6%.
Embodiment 2
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl2·4H2O、FeCl3·6H2O
It is the corresponding addition 18.75gFeCl of every liter of distilled water with the addition of distilled water2·4H2O, adds 56.25g FeCl3·6H2O,
Reacted under nitrogen protective condition in ultrasonic wave, while being warming up to 75 DEG C, NH is added after constant temperature3·H2O (every liter of distilled water
Add 125mLNH3·H2O), continue to obtain solidliquid mixture after reacting 20min, it is sharp after after the solidliquid mixture natural cooling
The magnetisable material in solidliquid mixture is adsorbed with magnet, cyclic washing then is carried out to the magnetisable material that absorption is obtained,
After 5h is dried under conditions of temperature is 65 DEG C, magnetic Fe is obtained3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.34: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
It is 100g/L calcium chloride for 0.75 citric acid, solid-to-liquid ratio, accounts for 12% magnetic Fe of solid material quality3O4Shaken in ultrasonic wave
Swing, temperature is filtering after crystallization 5h under conditions of 85 DEG C, natural cooling, it is 9~10 to adopt and be washed with distilled water to the pH value of product,
Then 5h is dried under conditions of temperature is 110 DEG C, obtains magnetic 5A molecular sieves.
Fig. 4 is infrared spectrum (FTIR) figure of magnetic 5A molecular sieves prepared by the present embodiment 2, by analyzing Fig. 4,
Magnetic 5A molecular sieves manufactured in the present embodiment are typical A type molecular sieve structure, are had with standard sample collection of illustrative plates much like red
Outer skeleton vibrational band.Wherein 528cm-1The absworption peak that place occurs corresponds to double Fourth Ring eigen vibrations of magnetic 5A molecular sieves,
852cm-1The absworption peak that place occurs corresponds to the not right of silicon-oxy tetrahedron and aluminum-oxygen tetrahedron in magnetic 5A molecular sieve structure skeletons
Claim stretching vibration, 1267cm-1The absworption peak of appearance corresponds to the flexural vibrations of water hydroxyl, 2572cm-1Locate the absworption peak pair occurred
Should be in the stretching vibration of surface water hydroxyl.Meanwhile, pass through magnet adsorption magnetic 5A molecular sieve qualitative analyses manufactured in the present embodiment
Magnetic property, test result shows that magnetic 5A molecular sieves manufactured in the present embodiment have good magnetic property, are easy to after recycling
Come into operation again.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 94.3%.
Embodiment 3
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl2·4H2O、FeCl3·6H2O
It is the corresponding addition 31.25gFeCl of every liter of distilled water with the addition of distilled water2·4H2O, adds 68.75g FeCl3·6H2O；
Reacted under nitrogen protective condition in ultrasonic wave, while being warming up to 85 DEG C, NH is added after constant temperature3·H2O (every liter of distilled water
Add 125mLNH3·H2O)；Continue to obtain solidliquid mixture after reacting 20min, it is sharp after after the solidliquid mixture natural cooling
The magnetisable material in solidliquid mixture is adsorbed with magnet, cyclic washing then is carried out to the magnetisable material that absorption is obtained,
After 5h is dried under conditions of temperature is 75 DEG C, magnetic Fe is obtained3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.36: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
It is 100g/L calcium chloride for 0.85 citric acid, solid-to-liquid ratio, accounts for 15% magnetic Fe of solid material quality3O4, shaken in ultrasonic wave
Swing, temperature is filtering after crystallization 4h under conditions of 95 DEG C, natural cooling, it is 9~10 to adopt and be washed with distilled water to the pH value of product,
Then 5h is dried under conditions of temperature is 110 DEG C, obtains magnetic 5A molecular sieves.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 93.2%.
Embodiment 4
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl3·6H2O and distilled water plus
Enter amount and add 31.25gFeCl for every liter of distilled water correspondence2·4H2O, adds 68.75g FeCl3·6H2O；Nitrogen protective condition
Under reacted in ultrasonic wave, while being warming up to 85 DEG C, NH is added after constant temperature3·H2(every liter of distilled water is added O
125mLNH3·H2O)；Continue to obtain solidliquid mixture after reacting 30min, after after the solidliquid mixture natural cooling, utilize magnetic
Iron is adsorbed to the magnetisable material in solidliquid mixture, then cyclic washing is carried out to the magnetisable material that absorption is obtained, in temperature
Spend to be dried under conditions of 65 DEG C after 5h, obtain magnetic Fe3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.35: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
The calcium chloride for being 200g/L for 0.65 citric acid, solid-to-liquid ratio, 15% magnetic Fe for accounting for solid material quality3O4, in ultrasonic wave
Vibration, temperature is crystallization 4h under conditions of 75 DEG C, is filtered after natural cooling, adopt be washed with distilled water to the pH value of product for 9~
10,5h then is dried under conditions of temperature is 110 DEG C, magnetic 5A molecular sieves are obtained.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 93.7%.
Embodiment 5
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl2·4H2O、FeCl3·6H2O
It is the corresponding addition 31.25gFeCl of every liter of distilled water with the addition of distilled water2·4H2O, adds 68.75g FeCl3·6H2O；
Reacted under nitrogen protective condition in ultrasonic wave, while being warming up to 75 DEG C, NH is added after constant temperature3·H2O (every liter of distilled water
Add 125mLNH3·H2O)；Continue to obtain solidliquid mixture after reacting 20min, it is sharp after after the solidliquid mixture natural cooling
The magnetisable material in solidliquid mixture is adsorbed with magnet, cyclic washing then is carried out to the magnetisable material that absorption is obtained,
After 5h is dried under conditions of temperature is 65 DEG C, magnetic Fe is obtained3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.36: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
It is 100g/L calcium chloride for 0.75 citric acid, solid-to-liquid ratio, accounts for 10% magnetic Fe of solid material quality3O4, shaken in ultrasonic wave
Swing, temperature is filtering after crystallization 4h under conditions of 95 DEG C, natural cooling, it is 9~10 to adopt and be washed with distilled water to the pH value of product,
Then 5h is dried under conditions of temperature is 110 DEG C, obtains magnetic 5A molecular sieves.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 94.1%.
Embodiment 6
The present embodiment prepares magnetic 5A molecular sieves and comprised the following steps：
Step 1: by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, FeCl2·4H2O、FeCl3·6H2O
It is the corresponding addition 31.25g FeCl of every liter of distilled water with the addition of distilled water2·4H2O, adds 68.75g FeCl3·6H2O,
Reacted under nitrogen protective condition in ultrasonic wave, while being warming up to 85 DEG C, NH is added after constant temperature3·H2O (every liter of distilled water
Add 125mLNH3H2O)；Continue to obtain solidliquid mixture after reacting 40min, after after the solidliquid mixture natural cooling,
The magnetisable material in solidliquid mixture is adsorbed using magnet, then the magnetisable material that absorption is obtained washed repeatedly
Wash, after 5h is dried under conditions of temperature is 65 DEG C, obtain magnetic Fe3O4；
Step 2: sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain molten
Liquid A, sodium metasilicate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B, then super
Under conditions of sonication, solution B is added drop-wise in solution A with 2.5mL/min drop rate, continues ultrasound after completion of dropping
Ripple vibrates 40min, obtains gel；The concentration of sodium metaaluminate is 96g/L in the solution A, and the concentration of sodium hydroxide is 20g/L,
The concentration of sodium metasilicate is 72g/L in the solution B, and the concentration of sodium hydroxide is 20g/L；Sodium metaaluminate and molten in the solution A
The mass ratio of sodium metasilicate is 1.36: 1 in liquid B；
Step 3: gel described in step 2 is placed in ultrasonic cleaner, C is then added6H8O7/Al2O3Mol ratio
It is 100g/L calcium chloride for 0.75 citric acid, solid-to-liquid ratio, accounts for 12% magnetic Fe of solid material quality3O4, shaken in ultrasonic wave
Swing, temperature is filtering after crystallization 4h under conditions of 85 DEG C, natural cooling, it is 9~10 to adopt and be washed with distilled water to the pH value of product,
Then 5h is dried under conditions of temperature is 110 DEG C, obtains magnetic 5A molecular sieves.
Using the magnetic 5A molecular sieves of spectrophotometry this implementation preparation to the absorption property of Pb In Exhausted Water ion, survey
The adsorption rate obtained reaches 93.5%.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art is substantially made to above example, still fall within technical solution of the present invention
Protection domain in.
Claims (10)
1. a kind of preparation method of magnetic 5A molecular sieves, it is characterised in that comprise the following steps：
1) by FeCl2·4H2O and FeCl3·6H2O is added in distilled water, under protective atmosphere, is reacted in ultrasonic wave, together
When be warming up to 75 DEG C~85 DEG C, NH is added after constant temperature3·H2O, continues fully reaction and obtains solidliquid mixture, by solidliquid mixture
After natural cooling, the magnetisable material in solidliquid mixture is adsorbed using magnet, washed, magnetic Fe is obtained after drying3O4；
2) sodium metaaluminate and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution A；By silicon
Sour sodium and sodium hydroxide are dissolved in distilled water, after being well mixed through supersonic oscillations, obtain solution B；Then in supersonic oscillations
Under conditions of, solution B is added drop-wise in solution A, continues supersonic oscillations after completion of dropping, gel is obtained；Meta-aluminic acid in solution A
The mass ratio of sodium metasilicate is (1.34~1.39) in sodium and solution B: 1；
3) citric acid, calcium chloride and magnetic Fe are added to gel3O4, Al in citric acid and gel2O3Mol ratio for 0.65~
0.85, calcium chloride is 90~100g/L, Fe with gel solid-to-liquid ratio3O4Addition be solid material quality 10%~15%；
Supersonic oscillations, temperature are crystallization under conditions of 75 DEG C~95 DEG C, and reaction terminates rear natural cooling and filtered, washing to production
The pH value of thing is 9~10, then dries, obtains magnetic 5A molecular sieves.
2. a kind of preparation method of magnetic 5A molecular sieves according to claim 1, it is characterised in that step 1) in：Raw material
Addition be：Every liter of distilled water adds (18.75~31.25) g FeCl2·4H2O, (56.25~68.75) g FeCl3·
6H2O, every liter of distilled water adds 125mL NH3·H2O。
3. the preparation method of a kind of magnetic 5A molecular sieves according to claim 1, it is characterised in that in step 1), ultrasound
The power of ripple reaction is 100W, adds NH3·H2Continue to react 20min~40min after O.
4. the preparation method of a kind of magnetic 5A molecular sieves according to claim 1, it is characterised in that in step 1), is dried
Temperature is 65 DEG C~75 DEG C, and the time is 5h~6h.
5. the preparation method of a kind of magnetic 5A molecular sieves according to claim 1, it is characterised in that in the solution A partially
The concentration of sodium aluminate is 96g/L~100g/L, and the concentration of sodium hydroxide is 20g/L~28g/L；Sodium metasilicate in the solution B
Concentration is 72g/L~76g/L, and the concentration of sodium hydroxide is 20g/L~28g/L.
6. a kind of preparation method of magnetic 5A molecular sieves according to claim 1, it is characterised in that step 2) in, solution B
It is added drop-wise to 2.5mL/min drop rate in solution A, continues supersonic oscillations 40min~60min after completion of dropping.
7. a kind of preparation method of magnetic 5A molecular sieves according to claim 1, it is characterised in that step 3) in, crystallization
Time is 2h~6h.
8. a kind of preparation method of magnetic 5A molecular sieves according to claim 1, it is characterised in that step 3) in, use
Water washing is distilled, then in 110 DEG C of dry 5h~6h.
9. magnetic 5A molecular sieves made from a kind of preparation method as described in any one in claim 1 to 8 are in absorption waste water
The application of middle heavy metal ion.
10. application according to claim 8, it is characterised in that for Adsorbing Lead Ion in Polluted Water.
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