CN1205121C - Synthesizing method for MOR zeolite comprising zinc - Google Patents
Synthesizing method for MOR zeolite comprising zinc Download PDFInfo
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- CN1205121C CN1205121C CN 03105400 CN03105400A CN1205121C CN 1205121 C CN1205121 C CN 1205121C CN 03105400 CN03105400 CN 03105400 CN 03105400 A CN03105400 A CN 03105400A CN 1205121 C CN1205121 C CN 1205121C
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Abstract
The present invention discloses a synthesis method for zinciferous MOR zeolite. In the method, water glass and fluorides are uniformly mixed; then, aluminum sources and zinc sources are added into the mixture; after being uniformly stirred, the mixture is crystallized for 1 to 6 days in a static state or a dynamic state at 120 to 220 DEG C. The synthesis method of the present invention has the advantages of reduced synthesis cost, simplified process and shortened time.
Description
Technical field
The invention relates to a kind of synthetic method of zeolite, the synthetic method of further saying so and containing zinc MOR zeolite about a kind of.
Background technology
Hetero-atom molecular-sieve is because of introducing heteroatoms in zeolite framework, can regulate sour kind, acid site intensity, acid site number and the duct of molecular sieve, because thereby the catalysis characteristics of heteroatoms self makes molecular sieve have unique catalytic performance, be widely used as the catalyzer of petrochemical complex and organic chemical industry's production process simultaneously.At present, about the research work of hetero-atom molecular-sieve and patent have a large amount of reports and verified, heteroatomss such as phosphorus, titanium, gallium, germanium, iron, vanadium all can be introduced into framework of molecular sieve, have synthesized many kinds of new catalytic materials.By secondary synthetic (Gu Gu gas-or liquid-method isomorphous substitution) also heteroatoms can be introduced framework of molecular sieve, but heteroatoms mainly concentrates on duct surface atom layer, and easily is deposited as non-cage heteroatom species on molecular sieve.The direct synthetic hetero-atom molecular-sieve of hydrothermal crystallization method, heteroatoms is the height homogeneously dispersed state on the whole, do not change the molecular sieve pore passage structure, need not carry out complicated aftertreatment, therefore have the incomparable superiority of other method of modifying (as pickling process, ion exchange method, vapour deposition process etc.).But because the restriction of heteroatoms self chemical property, the hetero-atom molecular-sieve building-up process generally need add organic formwork agent and strict control synthesis condition, and the degree of crystallinity of products therefrom generally all is lower than Si-Al zeolite.
Act on the catalytic performance that shows excellence in the aromatization owing to contain the double-function catalyzing of Zn molecular sieve, skeleton contains the synthetic of Zn molecular sieve and comes into one's own.Have that MFI, Beta, MOR are isostructural to be contained the synthetic of Zn molecular sieve and appear in the newspapers, for example, reported the zinciferous ZSM-5 molecular sieve of skeleton in " the synthetic and Study on influencing factors of heteroatoms Zn-ZSM-5 zeolite molecular sieve " (" Dalian University of Technology's journal " 1999,391 pages of 39 volumes) literary composition; Chinese patent ZL91111808.X discloses a kind of synthetic method of zinc-containing five-membered ring structure high-silicon zeolite, and this method adopts the synthetic zinciferous ZSM-5 molecular sieve of skeleton of xenocryst guiding method; In " Zn-Beta zeolite synthetic with characterize " (" the 7th national catalysis academic meeting paper summary collection " 1994 88 pages) literary composition, reported the synthetic of Zn-Beta zeolite.
Mordenite molecular sieve and synthetic method thereof that to disclose a kind of skeleton component in CN1304873A be silicon, zinc, aluminium, but used the organic amine template in this patent and with citric acid or Citrate trianion as complexing agent, its crystallization time is long.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art on the basis of existing technology, provide a kind of organic amine template of not using, the synthetic method that contains zinc MOR zeolite of work simplification.
Synthetic method provided by the invention comprises the steps:
1, fluorochemical, aluminium source and zinc source are made into the solution that concentration is 1～50 heavy % respectively;
2, fluoride aqueous solution is added stir in the water glass and obtain solution A, aluminium source and zinc source solution mix and obtain solution B, and B is added among the A, obtain gel C, and the reaction system mole consists of: SiO
2/ Al
2O
3=10～100, SiO
2/ ZnO=10～100, Na
2O/SiO
2=0.1～0.6, H
2O/SiO
2=10～60, F
-/ SiO
2=0.02～0.5;
3, gel C ageing under brute force stirs was packed into after 0.5～2 hour crystallizing kettle, static or stir under, 120 ℃～220 ℃ crystallization 1～6 day, obtain molecular sieve through the removal process of routine.
In the synthetic method provided by the invention, said fluorochemical is alkali-metal fluorochemical and/or Neutral ammonium fluoride, wherein said alkali-metal fluorochemical preferred fluorinated sodium; Said aluminium source is selected from Tai-Ace S 150, aluminum chloride, aluminum nitrate or aluminate, the preferred sodium metaaluminate of aluminate; Said zinc source is selected from zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
In the synthetic method provided by the invention, reaction system mole composition is preferably: SiO
2/ Al
2O
3=20～60, SiO
2/ ZnO=40～80, Na
2O/SiO
2=0.15～0.3, H
2O/SiO
2=20～40, F
-/ SiO
2=0.1～0.3.
In the synthetic method provided by the invention, in the step 3 said conventional removal process generally be meant with the crystallization thing after filtration, the process of deionized water wash after drying.
The advantage that synthetic method provided by the invention compared with prior art has is: owing to need not add any organic amine template, only in the presence of fluorochemical, make water glass, aluminium source and zinc source, therefore can reduce synthetic cost, simplify technology, shorten crystallization time.
Description of drawings
Accompanying drawing is the X-ray diffractogram of embodiment 1 synthetic MOR zeolite.
Embodiment
The following examples will be described further content of the present invention, but therefore not limit the scope of the invention.
Raw materials used except that specifying among the embodiment, all use chemically pure reagent.
The SiO of product among the embodiment
2/ Al
2O
3Mol ratio and ZnO content adopt Japanese Rigaku Denki Co., Ltd 3013 type XRF spectrometers to measure the characteristic curve intensity of Si-Al-Zn, obtain SiO in the molecular sieve
2/ Al
2O
3Mol ratio and ZnO content.
Embodiment 1
In 98.2 gram water glass (production of Zhou village catalyst plant), add 3.45 gram NaF and be dissolved in the solution of 100 gram water, under agitation slowly add 9 gram Al
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution that 50 gram water form and forms gel, stirs in the crystallizing kettle of packing into after half an hour gel is powerful, 175 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has MOR X zeolite RD chromatogram characteristic shown in Figure 1, and the MOR zeolite of putting down in writing with International Zeolite Association website (www.iza-online.org) has identical XRD spectra feature, illustrates that institute's sintetics is a mordenite, its SiO
2/ Al
2O
3Mol ratio is 17.4, and ZnO content is 3.4 heavy %.
The mole of reaction system consists of: SiO
2/ Al
2O
3=27, SiO
2/ ZnO=43.6, Na
2O/SiO
2=0.163, H
2O/SiO
2=35, F
-/ SiO
2=0.22
Embodiment 2
In 98.2 gram water glass, add 3 gram NH
4F is dissolved in the solution in the 100 gram water, under agitation adds 9 gram Al slowly
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 175 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 18, and ZnO content is 3.5 heavy %.
The mole of reaction system is formed with example 1.
Embodiment 3
In 98.2 gram water glass, add 3.45 gram NaF and be dissolved in 100 solution that restrain in the water, under agitation add 9 gram Al slowly
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 150 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 15.3, and ZnO content is 3.0 heavy %.
The mole of reaction system is formed with embodiment 1.
Embodiment 4
In 98.2 gram water glass, add 3.45 gram NaF and be dissolved in 100 solution that restrain in the water, under agitation add 9 gram Al slowly
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 175 ℃ of following crystallization 48 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 16.8, and ZnO content is 3.2 heavy %.
The mole of reaction system is formed with example 1.
Embodiment 5
In 98.2 gram water glass, add 3.45 gram NaF and be dissolved in 100 solution that restrain in the water, under agitation add 9 gram Al slowly
2(SO
4)
318H
2O and 1.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 175 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 17.5, and ZnO content is 2.1 heavy %.
The mole of reaction system consists of: SiO
2/ Al
2O
3=27, SiO
2/ ZnO=72.7, Na
2O/SiO
2=0.172, H
2O/SiO
2=35, F
-/ SiO
2=0.22.
Embodiment 6
In 98.2 gram water glass, add 3.45 gram NaF and be dissolved in 100 solution that restrain in the water, under agitation add 4.5 gram Al slowly
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 175 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 34.2, and ZnO content is 3.6 heavy %.
The mole of reaction system consists of: SiO
2/ Al
2O
3=54, SiO
2/ ZnO=43.6, Na
2O/SiO
2=0.22, H
2O/SiO
2=35, F
-/ SiO
2=0.22.
Embodiment 7
In 98.2 gram water glass, add 1.75 gram NaF and be dissolved in 100 solution that restrain in the water, under agitation add 4.5 gram Al slowly
2(SO
4)
318H
2O and 2.5 gram Zn (NO
3)
26H
2O is dissolved in the solution of 50 grams in the water, stirs in the crystallizing kettle of packing into after half an hour the gel that forms is powerful, 175 ℃ of following crystallization 72 hours, promptly gets zeolite of the present invention after washing, drying.The synthetic zeolite has XRD spectra feature shown in Figure 1, its SiO
2/ Al
2O
3Mol ratio is 26.6, and ZnO content is 2.8 heavy %.
The mole of reaction system consists of: SiO
2/ Al
2O
3=54, SiO
2/ ZnO=43.6, Na
2O/SiO
2=0.22, H
2O/SiO
2=35, F
-/ SiO
2=0.11.
Claims (6)
1, a kind of synthetic method that contains zinc MOR zeolite is characterized in that this synthetic method comprises the steps:
(1), fluorochemical, aluminium source and zinc source are made into the solution that concentration is 1～50 heavy % respectively, wherein said fluorochemical is alkali-metal fluorochemical and/or Neutral ammonium fluoride;
(2), fluoride aqueous solution is added in the water glass, stir, obtain solution A, aluminium source and zinc source solution are mixed, obtain solution B, B is added obtain gel C among the A;
(3), with gel C ageing under brute force stirs crystallizing kettle of packing into after 0.5～2 hour, static or stir down 120 ℃～220 ℃ crystallization 1～6 day, reclaim and obtain molecular sieve, wherein, the reaction system mole consists of: SiO
2/ Al
2O
3=10～100, SiO
2/ ZnO=10～100, Na
2O/SiO
2=0.1～0.6, H
2O/SiO
2=10～60, F
-/ SiO
2=0.02～0.5.
2, in accordance with the method for claim 1, wherein said alkali-metal fluorochemical is a Sodium Fluoride.
3, in accordance with the method for claim 1, wherein said aluminium source is selected from Tai-Ace S 150, aluminum chloride, aluminum nitrate or aluminate.
4, in accordance with the method for claim 3, wherein said aluminate is a sodium metaaluminate.
5, in accordance with the method for claim 1, wherein said zinc source is selected from zinc nitrate, zinc acetate, zinc chloride or zinc sulfate.
6, in accordance with the method for claim 1, wherein said reaction system mole consists of:
SiO
2/Al
2O
3＝20～60、SiO
2/ZnO＝40～80、Na
2O/SiO
2＝0.15～0.3、
H
2O/SiO
2＝20～40、F
-/SiO
2＝0.1～0.3。
Priority Applications (1)
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|---|---|---|---|
| CN 03105400 CN1205121C (en) | 2003-02-28 | 2003-02-28 | Synthesizing method for MOR zeolite comprising zinc |
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|---|---|---|---|
| CN 03105400 CN1205121C (en) | 2003-02-28 | 2003-02-28 | Synthesizing method for MOR zeolite comprising zinc |
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|---|---|
| CN1524788A CN1524788A (en) | 2004-09-01 |
| CN1205121C true CN1205121C (en) | 2005-06-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014174416A2 (en) * | 2013-04-22 | 2014-10-30 | Basf Se | Dehydration of sugars on zeolites obtainable from an organotemplate-free synthetic process |
| WO2018103089A1 (en) * | 2016-12-09 | 2018-06-14 | 中国科学院大连化学物理研究所 | Method for synthesizing mordenite mor molecular sieve, and product and use thereof |
| CN113200554A (en) * | 2021-05-07 | 2021-08-03 | 中国矿业大学 | Nano mordenite molecular sieve and preparation method and application thereof |
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