CN102311126B - Method for preparing NU-87 molecular sieve - Google Patents
Method for preparing NU-87 molecular sieve Download PDFInfo
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- CN102311126B CN102311126B CN 201010221168 CN201010221168A CN102311126B CN 102311126 B CN102311126 B CN 102311126B CN 201010221168 CN201010221168 CN 201010221168 CN 201010221168 A CN201010221168 A CN 201010221168A CN 102311126 B CN102311126 B CN 102311126B
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Abstract
The invention discloses a method for preparing an NU-87 molecular sieve. The method comprises a crystallized material preparing process, a crystallizing process, and a crystallized product recycling process, and is characterized in that: in the crystallizing process, organic acid and inorganic base are added in sequence; after the organic acid is added for crystallizing for 1 to 8 days, the inorganic base is added; the adding amount of the inorganic base accords with a condition that the inorganic base has the concentration of 0.5 to 1.2mol/L in crystallization synthesis system materials; the crystallization is hydrothermal crystallization; and the crystallization temperature is 80 to 200DEG C. By the method, mixed crystals such as mordenite, quartz and the like can be inhibited from being generated, the crystallinity of the NU-87 molecular sieve is improved, a synthetic proportioning range of the NU-87 molecular sieve is widened, and the NU-87 molecular sieve has flexible adjustability.
Description
Technical field
The present invention relates to a kind of preparation method of NU-87 molecular sieve.
Background technology
The NU-87 molecular sieve has NES type topological framework, is the supersiliceous zeolite molecular sieve of two-dimentional microvoid structure.It is to be that 10 yuan of the 0.47nm * 0.60nm parallel ducts of ring and diameter are the two-dimentional micropore system that the twelve-ring duct of 0.53nm * 0.68nm intersects to form by diameter, and only communicates with the external world by ten-ring duct window.This special structure shows again the feature of twelve-ring so that the NU-87 molecular sieve had both shown the feature of ten-ring in some catalyzed reaction.NES type structure molecular screen has special physical and chemical performance, shows unique catalytic performance in the reactions such as alkylation, isomerization, disproportionation.
European patent EP 377291 and US Patent No. 5041402 have proposed NU-87 molecular sieve and preparation method thereof the earliest.Concrete synthetic method is as follows: aluminium source, alkali and inorganic salt are dissolved in the part water make solution A, template is dissolved in the part water makes solution B, the silicon source is dissolved in the water makes solution C; At first solution B is joined in the solution A, stir, then solution C is joined in the solution A, stir; At last at the synthetic NU-87 molecular sieve of 180 ℃ of lower crystallization 257～451h.Each molar ratio of material that adds is SiO
2/ Al
2O
3=20～200, Na
2O/SiO
2=0.1～0.5, R/SiO
2=0.05～0.5, H
2O/SiO
2=25～75, NaL/SiO
2=0～0.25, wherein R is the template C-10, and NaL is sodium salt.US Patent No. 5102641 also discloses a kind of preparation method of NU-87 molecular sieve, its synthetic method and US Patent No. 5041402 not too large differences, the template that just adopts is C-10, bromination dodecane diamine, bromination octane diamine, enlarged the kind of template, and added the NU-87 molecular sieve as crystal seed in building-up process, crystallization time shortens to 130～192h.
Above-mentioned preparation NU-87 molecular sieve method, usually the stray crystals such as association mordenite, quartz reduce the degree of crystallinity of NU-87 molecular sieve; In addition, the method also exists the ratio range of synthesis material narrower, the poor deficiency that waits of the modulation of NU-87 molecular sieve.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of the high NU-87 molecular sieve of a kind of degree of crystallinity.
The preparation method of NU-87 molecular sieve of the present invention, comprise crystallization material process for preparation, crystallization process and crystallization product recycling process, wherein in crystallization process, add sequentially organic acid and mineral alkali, add the organic acid crystallization and add mineral alkali after 1～8 day, SiO in organic acid add-on and the crystallization material
2Mol ratio be 0.15: 1～0.5: 1, the add-on of mineral alkali is 0.5～1.2mol/L for the concentration of this mineral alkali in crystallization synthetic system material, crystallization adopts hydrothermal crystallization process, crystallization temperature is 80～200 ℃.
In the NU-87 molecular sieve preparation method of the present invention, crystallization is 2～8 days before crystallization process adds organic acid, and crystallization finished whole crystallization process in 2～8 days after adding mineral alkali.The adding mode of organic acid and mineral alkali can specifically be determined according to the situation of equipment, directly add organic acid (or mineral alkali) as can not stopping the thermostatic crystallization process, also can suspend the thermostatic crystallization process, after temperature is down to below 100 ℃, add, continue again crystallization process behind the adding organic acid (or mineral alkali).Adding indegree and can being respectively more than 1 time or 1 time of organic acid and mineral alkali in order to simplify the operation, generally gets final product by 1～5 adding.
In the NU-87 molecular sieve preparation method of the present invention, crystallization process can adopt static crystallization, also can adopt dynamic crystallization, the preferred latter, and dynamic crystallization generally adopts the mode of stirring to carry out.If the employing static crystallization also need stir behind adding organic acid or the mineral alkali.
In the NU-87 molecular sieve preparation method of the present invention, the organic acid of adding is one or more in oxalic acid, acetic acid, hexanodioic acid, tartrate, citric acid or the formic acid, is preferably acetic acid; The mineral alkali that adds is sodium hydroxide or potassium hydroxide.
In the NU-87 molecular sieve preparation method of the present invention, crystallization material process for preparation can adopt the various compound methods of crystallization material in the conventional NU-87 molecular sieve preparation method, preferably in crystallization material process for preparation, add strong aqua, the pH value of the hierarchy of control is 12.2～12.8, and each component by the mol ratio of its oxide compound or salt is in the crystallization material:
SiO
2/Al
2O
3＝20～200；
R/SiO
2＝0.05～1.0；
Na
2O/SiO
2＝0.05～0.6；
H
2O/SiO
2＝25～80；
NaL/SiO
2＝0.1～0.5
R is template bromination decamethonium, and NaL is a kind of sodium salt, can be sodium-chlor, Sodium Bromide, SODIUMNITRATE, sodium-acetate, sodium oxalate, is preferably sodium-chlor.The aluminium source can for one or more the mixture in aluminium salt, aluminate, aluminum oxide, aluminium hydroxide or the aluminium colloidal sol, be preferably sodium aluminate; Silicon source material can for White Carbon black, silicon sol, water glass or tetraethoxy etc., be preferably silicon sol.
After crystallization was finished, after filtration, washing and dry, roasting made the NU-87 molecular sieve.
The preparation method of NU-87 molecular sieve of the present invention has used respectively organic acid and mineral alkali in the different steps of crystallization.Experiment shows, by organic acid and mineral alkali the potential of hydrogen of crystallization process different steps is regulated, and has suppressed the generation of the stray crystals such as mordenite, quartz, has improved the degree of crystallinity of NU-87 molecular sieve, and the degree of crystallinity of sintetics generally can reach more than 95%.In addition, in crystallization material process for preparation, adopt the method for ammoniacal liquor hierarchy of control pH value, can enlarge the synthetic ratio scope of NU-87 molecular sieve, make the NU-87 molecular sieve have flexibly modulation.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 1 preparation.
Fig. 2 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 2 preparations.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 3 preparations.
Fig. 4 is X-ray diffraction (XRD) spectrogram of the molecular sieve of the embodiment of the invention 4 preparations.
Embodiment
A kind of concrete synthetic method of the present invention is as follows:
(1) preparation of crystallization raw mix gel:
Obtain solution 1: aluminium source, alkali, template and inorganic salt are joined in the distilled water by a certain percentage, under whipped state, mix.
Obtain solution 2: the silicon source is joined in the distilled water, under whipped state, mix.
Solution 2 is slowly joined in the solution 1, simultaneously can drip strong aqua, under whipped state, mix, make the synthetic material of gel crystallization, the synthetic material of the gained crystallization hydrothermal crystallizing device of packing into is carried out crystallization process.
(2) crystallization: a kind of concrete crystallization process is as follows, and at first 150～200 ℃ of lower crystallization 3～7 days, this process crystallization temperature can be adjusted, and also can carry out thermostatic crystallization; Then add a kind of organic acid by the feed pot on the crystallization system in synthetic system, acid can add when temperature is reduced to below 100 ℃, also can directly add in the thermostatic crystallization process, continues crystallization 3～7 days at 150～200 ℃; Add sodium hydroxide in the most backward synthetic system, the basicity of regulator solution was 80～190 ℃ of crystallization 6～24 hours.Crystallization process preferably carries out under dynamic condition, and the general mode that stirs that adopts is carried out, stirring velocity be generally 50～800rpm (rev/min), the different crystallization stages can be adopted identical stirring velocity, also can adopt different stirring velocitys.
(3) crystallization product recycling process: adopt conventional method and condition, such as steps such as filtration, washing, drying, roastings.
Further specify the present invention program and effect below by embodiment.
Embodiment 1
Obtain solution 1: in beaker, successively add 9.84g sodium hydroxide, 1.13g sodium aluminate (Al
2O
3Weight content is 45%), 75.06g bromination decamethonium, 5.36g sodium-chlor and 300ml distilled water, stir.Obtain solution 2: in beaker with 59.80g silicon sol (SiO
2Weight content is 30%) join in the 60ml distilled water, stir.Solution 2 is slowly joined in the solution 1, carry out the Dynamic Hydrothermal crystallization in the synthesis reactor of packing into after stirring.
At first 175 ℃ of crystallization 4.5 days, stirring velocity was 80rpm, then stirring velocity is brought up to 400rpm, be warming up to 190 ℃, continued crystallization 1 day, then temperature is reduced to 60 ℃, add 5.39g acetic acid, be warming up to 170 ℃ after stirring, continued crystallization 4 days, stirring velocity is 100rpm, reduce temperature to 80 ℃, add 11.25g sodium hydroxide, be warming up to 90 ℃ after stirring, crystallization time is 12 hours, and stirring velocity is 100rpm.
After crystallization was finished, after filtration, washing and dry, roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 98%.
Embodiment 2
Obtain solution 1: in beaker, successively add 10.74g sodium hydroxide, 1.13g sodium aluminate, 75.06g bromination decamethonium, 5.36g sodium-chlor and 330ml distilled water, stir.Obtain solution 2: in beaker, the 59.80g silicon sol is joined 50ml distilled water, stir.Solution 2 is slowly joined in the solution 1, and the pH value that drips simultaneously ammoniacal liquor control solution is 12.4.Pack into after stirring and carry out the Dynamic Hydrothermal crystallization in the synthesis reactor.
At first 180 ℃ of crystallization 4 days, stirring velocity was 80rpm, then stirring velocity is brought up to 400rpm, is warming up to 190 ℃, continue crystallization 1 day, and then temperature was reduced to 60 ℃, add 5.39g acetic acid, be warming up to 170 ℃ after stirring, continued crystallization 4 days, stirring velocity is 100rpm.Reduce temperature to 80 ℃, add 11.25g sodium hydroxide, be warming up to 90 ℃ after stirring, crystallization time is 12 hours, and stirring velocity is 100rpm.
After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 103%.
Embodiment 3
Obtain solution 1: in beaker, successively add 10.74g sodium hydroxide, 1.13g sodium aluminate, 75.06g bromination decamethonium, 5.36g sodium-chlor and 330ml distilled water, stir.Obtain solution 2: in beaker, the 59.80g silicon sol is joined 50ml distilled water, stir.Solution 2 is slowly joined in the solution 1, and the pH value that drips simultaneously ammoniacal liquor control solution is 12.2.Pack into after stirring and carry out the Dynamic Hydrothermal crystallization in the synthesis reactor.
At first 180 ℃ of crystallization 5 days, stirring velocity is 150rpm, then add 5.39g acetic acid, stirring velocity is brought up to 400rpm, be warming up to 195 ℃, continued crystallization 1 day, be cooled to 170 ℃, stirring velocity is 100rpm, and crystallization adds 11.25g sodium hydroxide after 4 days, stir, stirring velocity was increased to the 400rpm crystallization 1 day.
After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 101%.
Embodiment 4
Obtain solution 1: in beaker, successively add 9.66g sodium hydroxide, 1.13g sodium aluminate, 75.06g bromination decamethonium, 5.36g sodium-chlor and 300ml distilled water, stir.Obtain solution 2: in beaker, the 59.8g silicon sol is joined 50ml distilled water, stir.Solution 2 is slowly joined in the solution 1, and the pH value that drips simultaneously ammoniacal liquor control solution is 12.6.Pack into after stirring and carry out the Dynamic Hydrothermal crystallization in the synthesis reactor.
At first 165 ℃ of crystallization 5 days, stirring velocity was 80rpm, then stirring velocity is brought up to 400rpm, add 3.56g acetic acid, be warming up to 190 ℃, continued crystallization 1.5 days, temperature is reduced to 170 ℃, continued crystallization 4 days, stirring velocity is 100rpm, be cooled to 100 ℃, add 11.56g sodium hydroxide, continued crystallization 1 day, temperature is risen to 165 ℃, continued crystallization 5 days, stirring velocity is 100rpm.
After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 96%.
Obtain solution 1: in beaker, successively add 10.74g sodium hydroxide, 1.13g sodium aluminate, 75.06g bromination decamethonium, 5.36g sodium-chlor and 300ml distilled water, stir.Obtain solution 2: in beaker, the 59.8g silicon sol is joined 80ml distilled water, stir.Solution 2 is slowly joined in the solution 1, and the pH value that drips simultaneously ammoniacal liquor control solution is 12.3.Pack into after stirring and carry out the Dynamic Hydrothermal crystallization in the synthesis reactor.
At first 180 ℃ of crystallization 5 days, stirring velocity was 80rpm, and stirring velocity is brought up to 400rpm, be warming up to 185 ℃, continued crystallization 1 day, cool the temperature to 175 ℃, stirring velocity is reduced to 100rpm, adds 1.00g acetic acid, continues crystallization 1 day, then temperature is reduced to 170 ℃, add 2.36g acetic acid, continued crystallization 4 days, add at last 1.25g acetic acid, continued crystallization 12 hours, stirring velocity is 100rpm.Temperature rises to 170 ℃, adds 3.35g sodium hydroxide, the rear continuation crystallization that stirs 12 hours, and stirring velocity is 100rpm, reduces temperature to 90 ℃, adds 2.25g sodium hydroxide, and the rear crystallization time that stirs is 12 hours, and stirring velocity is 100rpm.
After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 100%.
Comparative example 1
Do not add acetic acid in the crystallization process, all the other conditions are identical with embodiment 3.After crystallization was finished, after filtration, washing and dry, roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 88%.
Comparative example 2
Do not add sodium hydroxide in the crystallization process, all the other conditions are identical with embodiment 3.After crystallization was finished, after filtration, washing and dry, roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 90%.
Comparative example 3
Namely do not add acetic acid in the crystallization process and also do not add sodium hydroxide, all the other conditions are identical with embodiment 3.After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 85%.
Comparative example 4
According to US Patent No. 5102641 preparation NU-87 molecular sieves, molecular sieve crystallinity is 80%.
Concrete preparation method is as follows:
Obtain solution 1: in beaker, successively add 10.74g sodium hydroxide, 1.13g sodium aluminate, 75.06g bromination decamethonium, 5.36g sodium-chlor and 300ml distilled water, stir.Obtain solution 2: in beaker, the 59.8g silicon sol is joined 50ml distilled water, stir.Solution 2 is slowly joined in the solution 1, in the synthesis reactor of packing into after stirring, in 180 ℃, 150rpm crystallization 8 days.
After crystallization was finished, after filtration, washing and dry, high-temperature roasting made the NU-87 molecular sieve.The degree of crystallinity of NU-87 molecular sieve is 80%.
Claims (7)
1. the preparation method of a NU-87 molecular sieve, comprise crystallization material process for preparation, crystallization process and crystallization product recycling process, it is characterized in that: in crystallization process, add sequentially organic acid and mineral alkali, add the organic acid crystallization and add mineral alkali after 1～8 day, SiO in organic acid add-on and the crystallization material
2Mol ratio be 0.15: 1～0.5: 1, the add-on of mineral alkali is 0.5～1.2mol/L for the concentration of this mineral alkali in crystallization synthetic system material, crystallization adopts hydrothermal crystallization process, crystallization temperature is 80～200 ℃, in crystallization material process for preparation, add strong aqua, the pH value of the hierarchy of control is 12.2～12.8, and each component by the mol ratio of its oxide compound or salt is in the crystallization material:
SiO
2/Al
2O
3＝20～200；
R/SiO
2＝0.05～1.0；
Na
2O/SiO
2＝0.05～0.6；
H
2O/SiO
2＝25～80；
NaL/SiO
2＝0.1～0.5
R is template bromination decamethonium, and NaL is a kind of sodium salt.
2. the method for claim 1 is characterized in that: crystallization is 2～8 days before crystallization process adds organic acid, and crystallization finished whole crystallization process in 2～8 days after adding mineral alkali.
3. the method for claim 1, it is characterized in that: organic acid and mineral alkali add after crystallization temperature is lower than 100 ℃ or directly add when thermostatic crystallization, continue crystallization process after adding organic acid or mineral alkali again.
4. the method for claim 1, it is characterized in that: the indegree that adds of organic acid and mineral alkali is respectively more than 1 time or 1 time.
5. the method for claim 1 is characterized in that: crystallization process adopts static crystallization or dynamic crystallization, and dynamic crystallization adopts the mode that stirs to carry out, and static crystallization also need stir after adding organic acid or mineral alkali.
6. the method for claim 1, it is characterized in that: described organic acid is one or more in oxalic acid, acetic acid, hexanodioic acid, tartrate, citric acid or the formic acid.
7. the method for claim 1, it is characterized in that: mineral alkali is sodium hydroxide or potassium hydroxide.
8, the method for claim 1 is characterized in that: the aluminium source is one or more in aluminium salt, aluminate, aluminum oxide, aluminium hydroxide or the aluminium colloidal sol, and silicon source material is White Carbon black, silicon sol, water glass or tetraethoxy.
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Non-Patent Citations (4)
| Title |
|---|
| 《一种新型的高硅沸石NU-87的合成与表征》;王丽丽等;《分子催化》;20070831;第21卷;MC617-MC618 * |
| 《含NES型分子筛的研究进展》;陈媛媛等;《综述专论》;20091231;第17卷(第5期);第63-68页 * |
| 王丽丽等.《一种新型的高硅沸石NU-87的合成与表征》.《分子催化》.2007,第21卷MC617-MC618. |
| 陈媛媛等.《含NES型分子筛的研究进展》.《综述专论》.2009,第17卷(第5期),第63-68页. |
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