CN106745044A - One kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve - Google Patents
One kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve Download PDFInfo
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Abstract
The present invention relates to inorganic material molecular sieve powder preparing technical field, it is desirable to provide a kind of to widen the method that low silica-alumina ratio X-type zeolite molecular sieve synthesizes scope.The method is specifically that one kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, comprises the following steps：（1）Prepare directed agents：Silicon source is added in silicon source, alkali source and water, directed agents are prepared；（2）Synthesizing low silicon aluminum ratio X-type molecular sieve original powder is aided in using Na2CO3.By the present invention in that using Na2CO3Auxiliary has synthesized pure phase and the preferable low silica-alumina ratio X-type molecular sieve of crystallinity；The Na2CO3 raw materials of use are that corrosivity is weaker, cheap and easy to get, are adapted to the raw material of industry of large-scale production and application；Especially the alkalescence of Na2CO3 raw materials is weaker, and the stabilization of basicity can be kept in broader synthetic ratio opereating specification, realizes the fine modulation of reaction system basicity.
Description
Technical field
The present invention relates to inorganic material-molecular sieve powder preparing technical field, specifically one kind uses Na2CO3Auxiliary synthesis
The method of low silica-alumina ratio X-type molecular sieve.
Background technology
Low silica-alumina ratio X-type molecular sieve is a kind of with a cube molecular sieve for faujasite structure, silica alumina ratio n (SiO2)/n
(Al2O3)=2.0~2.2.Low silica-alumina ratio X-type molecular sieve is by Li+The Li-LSX type molecular sieves of exchange degree high are exchanged for, are had
Larger N2 adsorption capacity and nitrogen oxygen separating coefficient, absorption property is more excellent, be currently in pressure swing adsorption method making oxygen by air separation technology most
It is preferable adsorbent；Further, since n (the SiO of LSX type molecular sieves2)/n(Al2O3) low, tradable cation-bit increases therewith
Plus possibly even reach maximum, the performance that it is used as detergent builders also superior to 4A type molecular sieves, as catalyst or catalysis
Agent carrier is also bigger than common X-type molecular sieve to the modulation scope of catalytic performance, therefore, low silica-alumina ratio X-type molecular sieve is industrially
Have a wide range of applications.
The lot of domestic and international document report synthetic method of low silica-alumina ratio X-type molecular sieve, but due in sodium potassium system
The synthesis of low silica-alumina ratio X-type molecular sieve is to n (H2O/NaK change) is very sensitive, and scale is more general than excursion in synthetic ratio
All over very little [n (H2O/NaK)=16~17], can only be about in the range of 1 in width and change, being off slightly from will cause A types and S
The generation of type zeolite stray crystal phase, therefore the formula synthesis scope of low silica-alumina ratio X-type molecular sieve is narrower, it is extremely easy in preparation process
Generation stray crystal phase, synthesis difficulty is larger, is difficult to be obtained the molecular sieve powder of high-purity when especially mass producing.
The content of the invention
Present invention aim to address scale ratio excursion is small, molecular sieve is matched somebody with somebody in low silica-alumina ratio X-type molecular sieve proportioning
The big problem of Fang Hecheng narrow ranges, preparation difficulty, to solve the above problems, Na is used the invention provides one kind2CO3Auxiliary is closed
Into the method for low silica-alumina ratio X-type molecular sieve.
The present invention is achieved by the following technical solutions：One kind uses Na2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve
Method, comprise the following steps：
(1) directed agents are prepared：Silicon source is added in silicon source, alkali source and water, directed agents are prepared；
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder：
A, get the raw materials ready
It is in molar ratio:SiO2/Al2O3=1.9~2.3, Na2O/(Na2O+K2O)=0.73~0.8, H2O/SiO2=50
~69, H2O/(Na2O+K2)=11~16, O wherein Na2CO3/Na2The ratio of O=0.3~0.7 is fed intake, and respective amount is measured respectively
Silicon source, silicon source, alkali source and water as raw material；
B, plastic
Mix in silicon source, alkali source and water addition reactor and be completely dissolved successively under agitation, Ran Hou
Silicon source is added under stirring, 0.5~1h is stirred under room temperature condition, obtain mixture material, finally added in mixture material
Enter the directed agents of 3%~5% mass percent, 0.5~1h is stirred at ambient temperature carries out plastic；
C, aging and crystallization
After the completion of plastic, by mixture gel in 8~22h of static burn at 60~70 DEG C；After aging end, then will mixing
Thing gel be placed in 100 DEG C at 3~4h of static crystallization；
D, it is filtered, washed and dried
After the completion of crystallization, slurry is separated into solid molecular sieves and mother liquor, solid product is washed with water to neutrality, in 100
Dried at DEG C, obtain final product and use Na2CO3Aid in the low silica-alumina ratio X-type molecular sieve of synthesis.
Further, step (1) prepares the method for directed agents including being：Silicon source and alkali source are first added to the water stirring to complete
Dissolving obtains high alkalinity sodium aluminate solution, and then silicon source is slowly added into high alkalinity sodium aluminate, after stirring at room temperature,
15 DEG C~30 DEG C 8~16h of static placement, obtain final product required directed agents；The mol ratio of each raw material is Na wherein in directed agents2O:SiO2:
Al2O3:H2O=17:5.76:1:250.
Further, the alkali source in step (1) is solid sodium hydroxide or sodium hydrate aqueous solution.
Further, the alkali source in described step (2) is the solid mixing of natrium carbonicum calcinatum, NaOH and potassium hydroxide
Thing, or three's mixture solution.
Further, the silicon source in step (1) and (2) is the aqueous solution of sodium metasilicate or sodium metasilicate.
Further, the silicon source in step (1) and (2) is the aqueous solution of sodium aluminate or sodium aluminate.
Use Na provided by the present invention2CO3Aid in the method for synthesizing low silicon aluminum ratio X-type molecular sieve compared with prior art,
Have the advantages that：
1st, the present invention using two one-step hydrothermals in sodium potassium system, adds directed agents in the range of said ratio, static old
Change and crystallization, SiO is finally obtained2/Al2O3Mol ratio be 2.0~2.2 between, crystallite dimension is the low silicon of pure phase between 1~3 μm
Aluminum ratio X-type molecular sieve.
2nd, the Na used in the present invention2CO3Raw material alkalescence is relatively weak, can be protected in broader synthetic ratio opereating specification
The stabilization of basicity is held, the fine modulation of system basicity is realized.Such that it is able to effectively widen the synthesis zone of low silica-alumina ratio X-type molecular sieve
Between, production difficulty is reduced, be conducive to industrialized production to improve.
3rd, the Na used in the present invention2CO3Raw material is weaker, the cheap and easy to get raw material of industry of corrosivity, reduces and is produced into
This.
Brief description of the drawings
Fig. 1 is the XRD spectrum of sample synthesized by embodiment 1 to 3.
Fig. 2 is the XRD spectrum of sample synthesized by embodiment 4 to 6.
Fig. 3 is the SEM figures of sample synthesized by embodiment 3.
Specific embodiment
Synthesized using two one-step hydrothermals in embodiment, with sodium silicate solution (SiO2313g/L, Na2O 100g/L) it is silicon
Source, with sodium aluminate (Al2O341%, Na2O 35%) it is silicon source, with sodium carbonate (Na2CO399.8%), NaOH (NaOH
96%), potassium hydroxide (KOH 85%) is sodium potassium basic materials, a series of molecular sieve samples of static monitor in stainless steel cauldron
Product.
Embodiment 1：
One kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
Under agitation successively by 1.382g sodium aluminate solids (Al2O30.0056mol, Na2O 0.0078mol)、
6.396g NaOH (0.0768mol) is added in 18.6ml deionized waters, obtains high alkalinity sodium aluminate solution, then will
6.4ml sodium silicate solutions (SiO20.032mol, Na2O 0.01mol) it is slowly added in high alkalinity sodium aluminate solution, at room temperature
Stirring 0.5h, directed agents are after aging 9h is stood under the conditions of 25 DEG C.Na2O:SiO2:Al2O3:H2O=0.0946:0.032:
0.0056:1.3889=17:5.76:1:250, the calculating of the amount of the material of its reclaimed water is：(6.4+18.6)/18=
1.3889mol。
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates (Al2O30.0100mol, Na2O 0.0140mol)、5.069g
Natrium carbonicum calcinatum (Na2CO30.0477mol, Na2O 0.0477mol), 2.292g solid sodium hydroxides (Na2O
0.0275mol), 3.144g solid potassium hydroxides (K2O 0.0239mol) add 19.8ml (H2O1.1000mol) in deionized water
Stirring is then slowly added into 3.83ml sodium silicate solutions (SiO to being completely dissolved20.0200mol, Na2O 0.0062mol), room temperature
Lower stirring 0.5h, is eventually adding the directed agents for accounting for reactant gross mass 4%, continues to stir 0.5h under room temperature condition；By reactant
In static burn in 8h at 60 DEG C, in static crystallization 3h at 100 DEG C；After the completion of crystallization, slurry is separated into solid molecular sieves and mother
Liquid, solid product is washed with water to neutrality, in being dried at 100 DEG C, product is obtained final product after the completion of drying.The XRD of obtained product
Spectrum, silica alumina ratio and relative crystallinity are shown in Fig. 1 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.8, H2O/SiO2=
65.6,H2O/(Na2O+K2O)=11, Na2CO3/Na2O=0.5.
Embodiment 2：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
1.382g sodium aluminate solids, 6.396g NaOH are added into 18.6ml deionized waters successively under agitation
In, high alkalinity sodium aluminate solution is obtained, then 6.4ml sodium silicate solutions are slowly added in high alkalinity sodium aluminate solution, in room
The lower stirring 0.5h of temperature, directed agents are after aging 10h is stood under the conditions of 25 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates (Al2O30.0100mol, Na2O 0.0140mol)、4.559g
Natrium carbonicum calcinatum (Na2CO30.0429mol, Na2O 0.0429mol), 1.893g solid sodium hydroxides (Na2O
0.0227mol), 3.099g solid potassium hydroxides (K2O 0.0235mol) add 19.8ml deionized waters (H2O 1.1000mol)
Middle stirring is then slowly added into 3.83ml sodium silicate solutions (SiO to being completely dissolved20.0200mol, Na2O 0.0062mol), room
The lower stirring 0.5h of temperature, is eventually adding the directed agents for accounting for reactant gross mass 3%, continues to stir 0.5h under room temperature condition；Will reaction
Thing in static burn in 10h at 60 DEG C, in static crystallization 3.5h at 100 DEG C；After the completion of crystallization, slurry is separated into solid molecular sieves
And mother liquor, solid product is washed with water to neutrality, in being dried at 100 DEG C, product is obtained final product after the completion of drying.Obtained product
XRD spectrum, silica alumina ratio and relative crystallinity are shown in Fig. 1 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.785, H2O/SiO2
=65.6, H2O/(Na2O+K2O)=12, Na2CO3/Na2O=0.5.
Embodiment 3：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
1.382g sodium aluminate solids, 6.396g NaOH are added into 18.6ml deionized waters successively under agitation
In, high alkalinity sodium aluminate solution is obtained, then 6.4ml sodium silicate solutions are slowly added in high alkalinity sodium aluminate solution, in room
The lower stirring 0.5h of temperature, directed agents are after aging 8h is stood under the conditions of 30 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 4.129g natrium carbonicum calcinatums, 1.554g solid sodium hydroxides,
Stirred in 3.059g solid potassium hydroxides to being completely dissolved, be then slowly added into 3.83ml sodium silicate solutions, stirred at room temperature
0.5h, is eventually adding the directed agents for accounting for reactant gross mass 4%, continues to stir 0.5h under room temperature condition；By reactant in 65 DEG C
Lower static burn in 10h, in static crystallization 4h at 100 DEG C；After the completion of crystallization, slurry is separated into solid molecular sieves and mother liquor, Gu
Body product is washed with water to neutrality, in being dried at 100 DEG C, product is obtained final product after the completion of drying.The XRD spectrum of obtained product, SEM
Figure, silica alumina ratio and relative crystallinity are shown in Fig. 1, Fig. 3 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.77, H2O/SiO2=
65.6,H2O/(Na2O+K2O)=13, Na2CO3/Na2O=0.5.
Embodiment 4：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
1.382g sodium aluminate solids, 6.396g NaOH are added into 18.6ml deionized waters successively under agitation
In, high alkalinity sodium aluminate solution is obtained, then 6.4ml sodium silicate solutions are slowly added in high alkalinity sodium aluminate solution, in room
The lower stirring 0.5h of temperature, directed agents are after aging 12h is stood under the conditions of 25 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 3.768g natrium carbonicum calcinatums, 1.272g solid sodium hydroxides,
Stirred in 3.003g solid potassium hydroxides to being completely dissolved, be then slowly added into 3.83ml sodium silicate solutions, stirred at room temperature
0.5h, is eventually adding the directed agents for accounting for reactant gross mass 3%, continues to stir 0.5h under room temperature condition；By reactant in 60 DEG C
Lower static burn in 15h, in static crystallization 4h at 100 DEG C；After the completion of crystallization, slurry is separated into solid molecular sieves and mother liquor, Gu
Body product is washed with water to neutrality, in being dried at 100 DEG C, product is obtained final product after the completion of drying.The XRD spectrum of obtained product, silicon
Aluminum ratio and relative crystallinity are shown in Fig. 2 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.757, H2O/SiO2
=65.6, H2O/(Na2O+K2O)=14, Na2CO3/Na2O=0.5.
Embodiment 5：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
By known technology, 1.382g sodium aluminate solids, 6.396g NaOH are added successively under agitation
In 18.6ml deionized waters, high alkalinity sodium aluminate solution is obtained, 6.4ml sodium silicate solutions are then slowly added to high alkalinity aluminic acid
In sodium solution, 0.5h is stirred at room temperature, directed agents are after aging 9h is stood under the conditions of 28 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 3.452g natrium carbonicum calcinatums, 1.023g solid sodium hydroxides,
2.965g solid potassium hydroxides are stirred to being completely dissolved in adding 19.8ml deionized waters, are then slowly added into 3.83ml sodium metasilicate
Solution, stirs 0.5h at room temperature, is eventually adding the directed agents for accounting for reactant gross mass 5%, continues to stir 0.5h under room temperature condition；
By reactant in static burn in 8h at 70 DEG C, in static crystallization 3h at 100 DEG C；After the completion of crystallization, slurry is separated into solid point
Son sieve and mother liquor, solid product are washed with water to neutrality, in being dried at 100 DEG C, product are obtained final product after the completion of drying.Obtained product
XRD spectrum, silica alumina ratio and relative crystallinity see Fig. 2 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.743, H2O/SiO2
=65.6, H2O/(Na2O+K2O)=15, Na2CO3/Na2O=0.5.
Embodiment 6：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
By known technology, 1.382g sodium aluminate solids, 6.396g NaOH are added successively under agitation
In 18.6ml deionized waters, high alkalinity sodium aluminate solution is obtained, 6.4ml sodium silicate solutions are then slowly added to high alkalinity aluminic acid
In sodium solution, 0.5h is stirred at room temperature, directed agents are after aging 12h is stood under the conditions of 20 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 3.186g natrium carbonicum calcinatums, 0.815g solid sodium hydroxides,
2.903g solid potassium hydroxides are stirred to being completely dissolved in adding 19.8ml deionized waters, are then slowly added into 3.83ml sodium metasilicate
Solution, stirs 1.0h at room temperature, is eventually adding the directed agents for accounting for reactant gross mass 4%, continues to stir 0.5h under room temperature condition；
By reactant in static burn in 15h at 60 DEG C, in static crystallization 3.5h at 100 DEG C；After the completion of crystallization, slurry is separated into solid
Molecular sieve and mother liquor, solid product are washed with water to neutrality, in being dried at 100 DEG C, product are obtained final product after the completion of drying.Obtained product
The XRD spectrum of thing, silica alumina ratio and relative crystallinity are shown in Fig. 2 and Biao 1.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2, Na2O/(Na2O+K2O)=0.731, H2O/SiO2
=65.6, H2O/(Na2O+K2O)=16, Na2CO3/Na2O=0.5.
Embodiment 7：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
By known technology, 1.382g sodium aluminate solids, 6.396g NaOH are added successively under agitation
In 18.6ml deionized waters, high alkalinity sodium aluminate solution is obtained, 6.4ml sodium silicate solutions are then slowly added to high alkalinity aluminic acid
In sodium solution, 0.5h is stirred at room temperature, directed agents are after aging 15h is stood under the conditions of 15 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 2.528g natrium carbonicum calcinatums, 2.979g solid sodium hydroxides,
2.847g solid potassium hydroxides are stirred to being completely dissolved in adding 19.9ml deionized waters, are then slowly added into 3.64ml sodium metasilicate
Solution, stirs 0.5h at room temperature, is eventually adding the directed agents for accounting for reactant gross mass 5%, and room temperature condition continues lower stirring 1.0h；
By reactant in static burn in 22h at 60 DEG C, in static crystallization 3h at 100 DEG C；After the completion of crystallization, slurry is separated into solid point
Son sieve and mother liquor, solid product are washed with water to neutrality, in being dried at 100 DEG C, product are obtained final product after the completion of drying.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=1.9, Na2O/(Na2O+K2O)=0.786, H2O/
SiO2=69, H2O/(Na2O+K2O)=13, Na2CO3/Na2O=0.3.
Embodiment 8：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
By known technology, 1.382g sodium aluminate solids, 6.396g NaOH are added successively under agitation
In 18.6ml deionized waters, high alkalinity sodium aluminate solution is obtained, 6.4ml sodium silicate solutions are then slowly added to high alkalinity aluminic acid
In sodium solution, 0.5h is stirred at room temperature, directed agents are after aging 12h is stood under the conditions of 20 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 5.204g natrium carbonicum calcinatums, 0.040g solid sodium hydroxides,
2.306g solid potassium hydroxides are stirred to being completely dissolved in adding 19.6ml deionized waters, are then slowly added into 4.0ml sodium metasilicate
Solution, stirs 0.5h at room temperature, is eventually adding the directed agents for accounting for reactant gross mass 3%, continues to stir 0.5h under room temperature condition；
By reactant in static burn in 15h at 65 DEG C, in static crystallization 4h at 100 DEG C；After the completion of crystallization, slurry is separated into solid point
Son sieve and mother liquor, solid product are washed with water to neutrality, in being dried at 100 DEG C, product are obtained final product after the completion of drying.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2.1, Na2O/(Na2O+K2O)=0.8, H2O/SiO2
=62.5, H2O/(Na2O+K2O)=15, Na2CO3/Na2O=0.7.
Embodiment 9：
One kind uses Na2CO3The method of synthesizing low silicon aluminum ratio X-type molecular sieve, specifically includes following steps：
(1) directed agents are prepared
By known technology, 1.382g sodium aluminate solids, 6.396g NaOH are added successively under agitation
In 18.6ml deionized waters, high alkalinity sodium aluminate solution is obtained, 6.4ml sodium silicate solutions are then slowly added to high alkalinity aluminic acid
In sodium solution, 0.5h is stirred at room temperature, directed agents are after aging 8h is stood under the conditions of 30 DEG C.
(2) Na is used2CO3Auxiliary synthesizing low silicon aluminum ratio X-type molecular sieve original powder
Under agitation successively by 2.488g sodium aluminates, 3.532g natrium carbonicum calcinatums, 1.009g solid sodium hydroxides,
2.767g solid potassium hydroxides are stirred to being completely dissolved in adding 16.3ml deionized waters, are then slowly added into 4.4ml sodium metasilicate
Solution, stirs 0.5h at room temperature, is eventually adding the directed agents for accounting for reactant gross mass 4%, continues to stir 0.5h under room temperature condition；
By reactant in static burn in 20h at 60 DEG C, in static crystallization 3.5h at 100 DEG C；After the completion of crystallization, slurry is separated into solid
Molecular sieve and mother liquor, solid product are washed with water to neutrality, in being dried at 100 DEG C, product are obtained final product after the completion of drying.
The mol ratio of each raw material is in step (2):SiO2/Al2O3=2.3, Na2O/(Na2O+K2O)=0.76, H2O/SiO2
=50, H2O/(Na2O+K2O)=13.1, Na2CO3/Na2O=0.5.
The silica alumina ratio and relative crystallinity of the different instances synthetic sample of table 1
Note：XRD method n (SiO2/Al2O3) gained is calculated by empirical equation：
a0 It is the lattice constant of X-ray diffraction method determination sample.
Claims (6)
1. one kind uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, it is characterised in that comprise the following steps：
（1）Prepare directed agents：Silicon source is added in silicon source, alkali source and water, directed agents are prepared；
（2）Use Na2CO3Auxiliary synthesizing low silicon aluminum ratio X type molecular screen primary powders：
A, get the raw materials ready
It is in molar ratio:SiO2/Al2O3=1.9~2.3,Na2O/(Na2O+K2O)=0.73~0.8, H2O/SiO2=50~69,H2O/
(Na2O+K2)=11 ~ 16, O wherein Na2CO3/Na2The ratio of O=0.3 ~ 0.7 feeds intake, measure respectively the silicon source of respective amount, silicon source,
Alkali source and water are used as raw material；
B, plastic
Mix in silicon source, alkali source and water addition reactor and be completely dissolved, then in stirring successively under agitation
Silicon source is added under state, under room temperature condition stir 0.5 ~ 1h, obtain mixture material, finally in mixture material add 3% ~
The directed agents of 5% mass percent, 0.5 ~ 1h is stirred at ambient temperature carries out plastic；
C, aging and crystallization
After the completion of plastic, by mixture gel in 8 ~ 22h of static burn at 60 ~ 70 DEG C；After aging end, then by mixture gel
3 ~ 4h of static crystallization at being placed in 100 DEG C；
D, it is filtered, washed and dried
After the completion of crystallization, slurry is separated into solid molecular sieves and mother liquor, solid product is washed with water to neutrality, at 100 DEG C
Dry, obtain final product and use Na2CO3Aid in the low silica-alumina ratio X-type molecular sieve of synthesis.
2. one kind according to claim 1 uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, its feature
It is, step（1）The method of directed agents is prepared including being：Silicon source and alkali source are first added to the water stirring and obtain height to being completely dissolved
, then be slowly added into silicon source in high alkalinity sodium aluminate by basicity sodium aluminate solution, after stirring at room temperature, 15 DEG C ~ 30 DEG C
Static state places 8 ~ 16h, obtains final product required directed agents；The mol ratio of each raw material is Na wherein in directed agents2O:SiO2:Al2O3:H2O=
17:5.76:1:250。
3. one kind according to claim 1 and 2 uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, it is special
Levy and be, step（1）In alkali source be solid sodium hydroxide or sodium hydrate aqueous solution.
4. one kind according to claim 3 uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, its feature
It is, described step（2）In alkali source for natrium carbonicum calcinatum, NaOH and potassium hydroxide solid mixture, or
Three's mixture solution.
5. one kind according to claim 3 uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, its feature
It is, step（1）With（2）In silicon source be the aqueous solution of sodium metasilicate or sodium metasilicate.
6. one kind according to claim 3 uses Na2CO3The method for aiding in synthesizing low silicon aluminum ratio X-type molecular sieve, its feature
It is, step（1）With（2）In silicon source be the aqueous solution of sodium aluminate or sodium aluminate.
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| CN110627088A (en) * | 2018-06-21 | 2019-12-31 | 中国科学院大连化学物理研究所 | Recycling method of low-silicon X molecular sieve synthesis mother liquor |
| CN112645348A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | X molecular sieve and preparation method thereof |
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|---|---|---|---|---|
| CN1911800A (en) * | 2006-08-31 | 2007-02-14 | 北京科技大学 | Method for preparing white carbon black and pure zeolite molecular sieve using flyash |
| CN102874842A (en) * | 2012-10-26 | 2013-01-16 | 涟水水莲蓬新材料有限公司 | Preparation method of zsm-5 molecular sieve with small crystal grains and large crystal body |
| CN103204516A (en) * | 2013-04-09 | 2013-07-17 | 华东师范大学 | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1911800A (en) * | 2006-08-31 | 2007-02-14 | 北京科技大学 | Method for preparing white carbon black and pure zeolite molecular sieve using flyash |
| CN102874842A (en) * | 2012-10-26 | 2013-01-16 | 涟水水莲蓬新材料有限公司 | Preparation method of zsm-5 molecular sieve with small crystal grains and large crystal body |
| CN103204516A (en) * | 2013-04-09 | 2013-07-17 | 华东师范大学 | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110627088A (en) * | 2018-06-21 | 2019-12-31 | 中国科学院大连化学物理研究所 | Recycling method of low-silicon X molecular sieve synthesis mother liquor |
| CN112645348A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | X molecular sieve and preparation method thereof |
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