CN101549874A - Synthesizing process for improving generation rate of nano Y-shaped molecular sieve - Google Patents
Synthesizing process for improving generation rate of nano Y-shaped molecular sieve Download PDFInfo
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- CN101549874A CN101549874A CNA200910011450XA CN200910011450A CN101549874A CN 101549874 A CN101549874 A CN 101549874A CN A200910011450X A CNA200910011450X A CN A200910011450XA CN 200910011450 A CN200910011450 A CN 200910011450A CN 101549874 A CN101549874 A CN 101549874A
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Abstract
The invention relates to a synthesizing process for improving generation rate of a nano Y-shaped molecular sieve, which comprises the steps of: adding organic template reagent and aluminum source sequentially into deionized water under agitating condition, and when the reagent and the aluminum source are dissolved, then adding silicon source and natrium source; transferring the synthesizing system into a reaction kettle, then heating till the temperature is 90 to 130 DEG C, and then carrying out hydrothermal crystallization for 60 to 110 hours; separating the mixtures of solid and liquid, wherein mother liquor is kept and the solid is the nano Y-shaped molecular sieve; supplementing appropriate reaction material to the obtained mother liquor, then carrying out crystallization and solid and liquor separation continuously till obtain a nano Y-shaped molecular sieve and reaction mother liquor again; and repeatedly supplementing reaction material, and then carrying out crystallization and solid and liquor separation so as to improve the generation rate of the nano Y-shaped molecular sieve. The process effectively utilizes the materials of unreacted silicion, aluminum, organic template reagent and the like in the synthesizing system so as to improve the generation rate of the nano Y-shaped molecular sieve by more than 40 percent; simultaneously, the grain size of the product is less than 100nm, and the time of every crystallization is relatively short.
Description
Technical field
The present invention relates to a kind of synthesis technique that improves generation rate of nano Y-shaped molecular sieve, specifically a kind ofly utilize raw materials such as unreacted silicon, aluminium and organic formwork agent in the mother liquor, significantly improve the synthesis technique of generation rate of nano Y-shaped molecular sieve by the repeatedly crystallization method of replenishing raw material.
Background technology
The zeolite crystal size of industrial use is generally micron order, the duct of this molecular sieve analog is longer, and reactant and product molecule are bigger at the diffusional resistance of molecular sieve intracrystalline in catalyzed reaction, cause deep reaction easily, produce carbon distribution, so the deactivation rate of catalyzer is very fast.The grain-size that reduces molecular sieve then can effectively address this problem.Along with reducing of grain-size, the surface atom number of crystal grain and the body ratio of atomicity mutually increase rapidly, can demonstrate stronger volume effect, surface effects and quantum size effect, can produce the physicochemical property that some are different from the uniqueness of macroparticle.Studies show that, with the catalyzer of superfine molecular sieves preparation in the utilization ratio that improves catalyzer, strengthen the macromole conversion capability, reduce reaction depth, improve selectivity and reduce aspects such as coking and deactivation and all show superiority.
Usually utilize the reaction system of adding organic formwork agent synthesize particle diameter less than the nano Y-shaped molecular sieve of 100nm (Stud Surf Sci Catal, 125, Elsevier, Amsterdam, 1999, P.141; Micropor Mesopor Mater 74 (2004) 189).Adopt microwave heating also can synthesize the nano Y-shaped molecular sieve (CN1730391A) of particle diameter less than 100nm.But, in adding the system of organic formwork agent, during the synthesis of nano Y molecular sieve, must adopt very low sodium content, otherwise will produce stray crystal.And sodium ion is the crucial species that generate Y zeolite, and extremely low sodium content has determined synthetic nanometer Y molecular sieve productive rate very low (less than 8%, with the silicon source that adds in the raw material and the SiO in the aluminium source
2With Al
2O
3The quality sum is a benchmark), so still have a large amount of unreacted silicon, aluminium and organic formwork agent species in the mother liquor after the crystallization.Document (Micropor Mesopor Mater 96 (2006) 405) proposes additionally not introduce under the situation of sodium ion having, and improves the productive rate of nano Y-shaped molecular sieve by crystallization repeatedly.Yet the productive rate of nano Y-shaped molecular sieve is closely related with the amount of sodium ion, and they are not introducing under the situation of sodium ion once more, only makes productive rate improve about 0.4% by three crystallization.Document (Stud Surf SciCatal, 135, Elsevier, Amsterdam, 2001, P.151) significantly improved the productive rate of molecular sieve by the single crystallization method of repeatedly introducing sodium ion, but the Y zeolite crystal that this method will not generate is earlier in time separated, but be retained in the reaction system, cause these molecular sieve crystals that formed in follow-up crystallization process, excessively to be grown up, the particle diameter of product surpasses 100nm; always In addition, this method requires the timed interval of twice introducing sodium ion to reach 7 days stray crystals in the ability elimination product, causes synthesis cycle longer.
Summary of the invention
The purpose of this invention is to provide a kind of synthesis technique that improves generation rate of nano Y-shaped molecular sieve, this technology is by replenishing the repeatedly crystallization method of raw material, realized effectively utilizing raw materials such as unreacted silicon, aluminium and organic formwork agent in the synthetic system, the productive rate of nano Y-shaped molecular sieve is increased to more than 40%.
The invention provides a kind of synthesis technique that improves generation rate of nano Y-shaped molecular sieve, its synthesis step is as follows:
A) organic formwork agent, aluminium source are added under agitation condition in the deionized water successively, be stirred to the dissolving back and add the silicon source, fully stirring or heating make the transparent or semitransparent back of solution add the sodium source;
Wherein the mole proportioning of reaction raw materials is: SiO
2/ Al
2O
3=3.5～4.5, Na
2O/Al
2O
3=0.020～0.050, H
2O/Al
2O
3=230～270, organic formwork agent/Al
2O
3=4.0～5.0;
B) synthetic system that step a is obtained is transferred in the reactor, is warming up to 90～130 ℃ of following hydrothermal crystallizings 60～110 hours after airtight;
C) solidliquid mixture that step b crystallization is obtained separates, and the mother liquor that wherein obtains keeps, and solid is nano Y-shaped molecular sieve through washing, drying;
It is characterized in that:
D) replenish an amount of sodium source according to the proportioning among the step a in the mother liquor that previous step is obtained, the condition according to step b continues crystallization then, carries out solid-liquid separation after the crystallization, obtains nano Y-shaped molecular sieve and reaction mother liquor once more;
E) repeating step d makes accumulative total productive rate 〉=40% (the quality sum with silicon-dioxide in silicon source and the aluminium source and aluminium sesquioxide is a benchmark) of nano Y-shaped molecular sieve.
The synthesis technique of raising generation rate of nano Y-shaped molecular sieve provided by the invention according to the mole proportioning of above-mentioned reaction raw materials, adopts the feed way of step a in the mother liquor that obtains after carrying out step e, supply various reaction raw materials, repeating step b～e.
The synthesis technique of raising generation rate of nano Y-shaped molecular sieve provided by the invention, described organic formwork agent are Tetramethylammonium hydroxide TMAOH; The aluminium source is an aluminum isopropylate; The silicon source is at least a in silicon sol, white carbon black, the tetraethoxy; The sodium source is at least a in the soluble sodium salts such as NaOH, NaCl.
The present invention has following technique effect:
In the synthesis technique of the present invention, by the method for crystallization, separating for several times repeatedly, the molecular sieve crystal of having avoided forming is excessively grown up, and the products therefrom particle diameter is lower than 100nm; The single crystallization time is short, and the mother liquor after the crystallization is clear solution, can directly carry out crystallization after replenishing raw material, and twice crystallization can closely be connected, and saves generated time; Can only replenish the sodium source, also can replenish all the other raw materials, realize making full use of the purpose of each raw material, the productive rate of nano Y-shaped molecular sieve is increased to more than 40%; This technology has not only significantly reduced the synthetic cost of nano Y-shaped molecular sieve, has also reduced the synthesis mother liquid pollution on the environment.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1 synthesis of nano Y zeolite;
Fig. 2 is the laser particle size analysis result of embodiment 1 synthesis of nano Y zeolite;
Fig. 3 is the TEM photo of embodiment 1 synthesis of nano Y zeolite;
Fig. 4 is the XRD spectra of the former powder of embodiment 2 synthesis of nano Y zeolites;
Fig. 5 is the SEM photo of embodiment 2 synthesis of nano Y zeolites;
Fig. 6 is the XRD spectra of the former powder of embodiment 3 synthesis of nano Y zeolites.
Embodiment
Following examples will give further instruction to the present invention, but not thereby limiting the invention.
With 100 gram tetramethyl ammonium hydroxide solutions (25%) and 26.5 gram aluminum isopropylate (〉=24.7%Al
2O
3), add successively in the 216 gram deionized waters, be stirred to solution clarification back and add 50 gram tetraethoxy (〉=28.0%SiO
2), 0.2 gram sodium hydroxide.Make the mole proportioning that obtains reaction mixture be: SiO
2/ Al
2O
3=3.65, Na
2O/Al
2O
3=0.032, H
2O/Al
2O
3=249, TMAOH/Al
2O
3=4.30.Then this mixture is transferred in the reactor airtight back crystallization 85 hours under 100 ℃, dynamic condition.System after the crystallization is carried out centrifugation, and the solid product that obtains (S-A1) washing back keeps the mother liquor (M-A1) that obtains in 120 ℃ of oven dry 24 hours, and this is synthetic for the first time.In M-A1, add 0.2 gram sodium hydroxide, continued under 100 ℃, dynamic condition crystallization then 85 hours, the system after the crystallization is carried out centrifugation, the solid product that obtains (S-A2) washing back was in 120 ℃ of oven dry 24 hours, keep the mother liquor (M-A2) that obtains, this is synthetic for the second time.Identical process repeats (gained solid product remember successively make S-A1, S-A2, S-A3, S-A4, S-A5, S-A6, S-A7 and S-A8) eight times, and the XRD spectrum (Fig. 1) of products therefrom shows that eight times the synthetic sample is Y zeolite; Adopt the dynamic light scattering particle size instrument that these samples are carried out testing graininess, result (Fig. 2) shows that the particle diameter of the first five time synthetic product is about 40nm, and the particle diameter of back three synthetic products is at 40～60nm.Fig. 3 is the TEM photo of the 4th synthetic nano Y-shaped molecular sieve (S-A4).Through eight times synthetic after, the productive rate of molecular sieve (is benchmark with the silicon source that adds and the quality sum of silicon-dioxide in the aluminium source and aluminium sesquioxide) is 53%.
With 186 gram tetramethyl ammonium hydroxide solutions (25%) and 44 gram aluminum isopropylate (〉=24.7%Al
2O
3), add successively in the 328 gram deionized waters, be stirred to dissolving back and add 28 gram white carbon blacks, heat and be stirred to the transparent back of solution and add 0.2 gram sodium hydroxide.Make the mole proportioning that obtains reaction mixture be: SiO
2/ Al
2O
3=4.36, Na
2O/Al
2O
3=0.024, H
2O/Al
2O
3=240, TMAOH/Al
2O
3=4.78.Then this mixture is transferred in the reactor airtight back crystallization 100 hours under 100 ℃, dynamic condition.System after the crystallization is carried out centrifugation, and the solid product that obtains (S-B1) washing back keeps the mother liquor (M-B1) that obtains in 120 ℃ of oven dry 24 hours, and this is synthetic for the first time.In M-B1, add 0.20 gram sodium hydroxide, continued under 100 ℃, dynamic condition crystallization then 100 hours.System after the crystallization is carried out centrifugation, and the solid product that obtains (S-B2) washing back keeps the mother liquor (M-B2) that obtains in 120 ℃ of oven dry 24 hours, and this is synthetic for the second time.Repeat said process ten times (gained solid product remember successively make S-B1, S-B2, S-B3, S-B4, S-B5, S-B6, S-B7, S-B8, S-B9 and S-B10), the spectrum (Fig. 4) that obtains product X RD shows that ten times the synthetic sample is Y zeolite.The SEM characterization result shows that the particle diameter of institute's synthetic product is all less than 90nm, and particle size distribution is narrow.The SEM photo of the 4th synthetic product (S-B4) as shown in Figure 5.Through ten times synthetic after, the productive rate of nano Y-shaped molecular sieve is 44%.
In embodiment 2, in through the mother liquor after 10 crystallization, add 15 gram tetramethyl ammonium hydroxide solutions (25%), 22 gram aluminum isopropylate (〉=24.7%Al
2O
3), 42 gram silicon sol (30.4%SiO
2, 0.1%Al
2O
3, 0.1%Na
2O, 69.4%H
2O) and 0.29 the gram sodium-chlor.Make the mole proportioning of synthetic system be: SiO
2/ Al
2O
3=4.36, Na
2O/Al
2O
3=0.030, H
2O/Al
2O
3=260, TMAOH/Al
2O
3=4.78.Crystallization 100 hours under 115 ℃, dynamic condition then.System after the crystallization is carried out centrifugation, and the solid product that obtains (S-C1) washing back keeps the mother liquor (M-C1) that obtains in 120 ℃ of oven dry 24 hours, and this is synthetic for the first time.In M-C1, add 0.29g sodium-chlor, continued under 115 ℃ of whipped states crystallization then 100 hours, the system after the crystallization is carried out centrifugation, the solid product that obtains (S-C2) washing back was in 120 ℃ of oven dry 24 hours, keep the mother liquor (M-C2) that obtains, this is synthetic for the second time.Repeat said process six times (gained solid product remember successively make S-C1, S-C2, S-C3, S-C4, S-C5 and S-C6), the XRD spectrum (Fig. 6) that obtains product shows that six times the synthetic sample is Y zeolite.The SEM characterization result shows that the particle diameter of institute's synthetic product is all less than 90nm.Through six times synthetic after, the productive rate of molecular sieve is 66%.
Claims (8)
1, a kind of synthesis technique that improves generation rate of nano Y-shaped molecular sieve, its synthesis step is as follows:
A) organic formwork agent, aluminium source are added under agitation condition in the deionized water successively, be stirred to the dissolving back and add the silicon source, fully stirring or heating make the transparent or semitransparent back of solution add the sodium source;
Wherein the mole proportioning of reaction raw materials is: SiO
2/ Al
2O
3=3.5～4.5, Na
2O/Al
2O
3=0.020～0.050, H
2O/Al
2O
3=230～270, organic formwork agent/Al
2O
3=4.0～5.0;
B) synthetic system that step a is obtained is transferred in the reactor, is warming up to 90～130 ℃ of following hydrothermal crystallizings 60～110 hours after airtight;
C) solidliquid mixture that step b crystallization is obtained separates, and the mother liquor that wherein obtains keeps, and solid is nano Y-shaped molecular sieve through washing, drying;
It is characterized in that:
D) replenish the sodium source according to the proportioning among the step a in the mother liquor that previous step is obtained, the condition according to step b continues crystallization then, carries out solid-liquid separation after the crystallization, obtains nano Y-shaped molecular sieve and reaction mother liquor once more;
E) repeating step d makes accumulative total productive rate 〉=40% of nano Y-shaped molecular sieve.
2, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: in the mother liquor that after carrying out step e, obtains according to the mole proportioning of above-mentioned reaction raw materials, adopt the feed way of step a, supply various reaction raw materials, repeating step b～e.
3, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: described organic formwork agent is Tetramethylammonium hydroxide TMAOH.
4, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: described aluminium source is an aluminum isopropylate.
5, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: described silicon source is at least a in silicon sol, white carbon black, the tetraethoxy.
6, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: described sodium source is at least a in some soluble sodium salts of NaOH, NaCl.
7, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: the calculating of the accumulative total productive rate of described nano Y-shaped molecular sieve is that the quality sum with silicon-dioxide in silicon source and the aluminium source and aluminium sesquioxide is a benchmark.
8, according to the synthesis technique of the described raising generation rate of nano Y-shaped molecular sieve of claim 1, it is characterized in that: described synthetic nano Y-shaped molecular sieve crystal grain is below 100nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016029591A1 (en) * | 2014-08-28 | 2016-03-03 | 中国科学院大连化学物理研究所 | Method for preparing y-type molecular sieve having high silica-alumina ratio |
| CN106145155A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of prepare the method for high silica alumina ratio Y type molecular sieve, product and application thereof |
| CN106698460A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nano Y molecular sieve |
| WO2022148394A1 (en) * | 2021-01-07 | 2022-07-14 | 中国石油化工股份有限公司 | Y-type molecular sieve and synthesis method therefor |
-
2009
- 2009-05-08 CN CNA200910011450XA patent/CN101549874A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016029591A1 (en) * | 2014-08-28 | 2016-03-03 | 中国科学院大连化学物理研究所 | Method for preparing y-type molecular sieve having high silica-alumina ratio |
| AU2014404762B2 (en) * | 2014-08-28 | 2018-05-24 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing Y-type molecular sieve having high silica-alumina ratio |
| US10252917B2 (en) | 2014-08-28 | 2019-04-09 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for preparing Y type molecular sieve having high silica to alumina ratio |
| CN106145155A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院大连化学物理研究所 | A kind of prepare the method for high silica alumina ratio Y type molecular sieve, product and application thereof |
| CN106145155B (en) * | 2015-04-23 | 2019-02-15 | 中国科学院大连化学物理研究所 | A kind of method preparing high silica alumina ratio Y type molecular sieve, product and its application |
| CN106698460A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Synthesis method of nano Y molecular sieve |
| CN106698460B (en) * | 2015-11-12 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of synthetic method of nanometer of Y molecular sieve |
| WO2022148394A1 (en) * | 2021-01-07 | 2022-07-14 | 中国石油化工股份有限公司 | Y-type molecular sieve and synthesis method therefor |
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Open date: 20091007 |