CN101468805B - Method for synthesizing ZSM-5 molecular sieve - Google Patents
Method for synthesizing ZSM-5 molecular sieve Download PDFInfo
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- CN101468805B CN101468805B CN200710304108XA CN200710304108A CN101468805B CN 101468805 B CN101468805 B CN 101468805B CN 200710304108X A CN200710304108X A CN 200710304108XA CN 200710304108 A CN200710304108 A CN 200710304108A CN 101468805 B CN101468805 B CN 101468805B
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Abstract
The invention provides a method for synthesizing a ZSM-5 molecular sieve, which comprises: mixing a silicon source, an aluminum source, alkali and water to obtain a reaction mixture, and hydrating and crystallizing the reaction mixture, wherein the silicon source, the alkali and the water partially or completely select from mother liquids generated by preparing a titanium-silicon molecular sieve. The method for synthesizing the ZSM-5 molecular sieve can effectively utilize the mother liquids generated by preparing the titanium-silicon molecular sieve, reduce the pollution to the environment caused by discharging the mother liquids, and reduce the synthesizing cost of the ZSM-5 molecular sieve simultaneously.
Description
Technical field
The present invention relates to a kind of synthetic method of molecular sieve, relate in particular to a kind of synthetic method of ZSM-5 molecular sieve.
Background technology
The ZSM-5 molecular sieve from 1972 by since the MOBIL company invention, be widely used in a lot of fields of petrochemical complex, its technology of preparing also becomes the emphasis of research.From the employed raw material of preparation ZSM-5 molecular sieve, mainly comprise silicon source, aluminium source, alkali, water etc.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.This molecular sieve analog has excellent catalytic activity and selective paraffin oxidation performance to many organic oxidizing reactions.The preparation method of described HTS generally include will contain silicon source, titanium source, organic bases and/or basic oxide reaction mixture in autoclave at 130-200 ℃ of following hydrothermal crystallizing, filter then, wash, dry, roasting.Wherein, described silicon source can be tetraalkyl silicon ester, colloidal state SiO
2Or alkalimetal silicate, the titanium source can be hydrolyzable titanium compound, described organic bases can be a TPAOH.
Wherein, in the preparation process of HTS, after filtering step, can produce a large amount of mother liquors usually, contain not materials such as the silicon source that consumes, organic bases in this mother liquor.If this mother liquor is directly discarded, will cause environmental pollution; And carry out sewage disposal, then can increase the expense of sewage disposal again.In addition, if the direct depleted of the unemployed composition in the mother liquor is talked about, also can correspondingly increase the production cost of molecular sieve.Therefore, effectively utilizing mother liquor that the preparation HTS produces has great importance to the suitability for industrialized production of molecular sieve.
Summary of the invention
To the objective of the invention is the problem that effectively to handle the mother liquor that produces in the preparation HTS process effectively in order solving in the prior art, a kind of synthetic method of the ZSM-5 molecular sieve that can be effectively the mother liquor that produces in the preparation HTS process be utilized to be provided.
The present inventor finds that after deliberation the mother liquor that produces in the preparation HTS process can be directly used in the preparation of ZSM-5 molecular sieve.
The invention provides the synthetic method of ZSM-5 molecular sieve, this method comprises mixes silicon source, aluminium source, alkali and water, obtains reaction mixture, with this reaction mixture hydrothermal crystallizing, wherein, described silicon source, alkali and water partly or entirely derive from the preparation HTS time mother liquor that produced.
The synthetic method of ZSM-5 molecular sieve provided by the invention can effectively be utilized the mother liquor that the preparation HTS produces, and has reduced because of mother liquor discharging pollution on the environment, makes the synthetic cost of ZSM-5 molecular sieve reduce simultaneously.
Description of drawings
Fig. 1 represents X-ray diffraction (XRD) the crystalline phase figure of standard specimen.
Embodiment
The synthetic method of ZSM-5 molecular sieve of the present invention comprises mixes silicon source, aluminium source, alkali and water, obtain reaction mixture, with this reaction mixture hydrothermal crystallizing, wherein, described silicon source, alkali and water partly or entirely derive from the mother liquor that preparation is produced during HTS.
Mother liquor of the present invention is meant when the preparation HTS, after the reaction raw materials that will prepare HTS carries out hydrothermal crystallizing, by filtering the liquid that produces.Described HTS can be conventional various HTS, for example can be TS-1 HTS, TS-2 HTS or Ti-β HTS, and these HTS and their preparation method are conventionally known to one of skill in the art.
In the reaction mixture of the present invention, the consumption of described silicon source, aluminium source, alkali and water is conventionally known to one of skill in the art.As long as the consumption of described silicon source, aluminium source, alkali and water makes in the described reaction mixture, SiO
2/ Al
2O
3Mol ratio is 20-1000, Na
2O/SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2Mol ratio is that 5-20 gets final product.
Because when preparing HTS according to diverse ways, raw material consumption and reaction conditions have nothing in common with each other, therefore contained various compositions also are different in the mother liquor that finally obtains.The amount of silicon source, alkali and the water that contains in mother liquor satisfies mol ratio Na
2O/SiO
2=0.03-0.5, H
2O/SiO
2During=5-20, then only need in mother liquor, to add the aluminium source and adjust silica alumina ratio, make reaction mixture satisfy mol ratio SiO
2/ Al
2O
3=20-1000 gets final product.The amount of silicon source, alkali and the water that contains in mother liquor does not satisfy mol ratio Na
2O/SiO
2=0.03-0.5, H
2O/SiO
2During=5-20, then can add silicon source, alkali and water and adjust.In addition, need to prove basicity (Na in mother liquor
2O) under the too high situation, also can add acid and regulate described basicity.Described acid can be sulfuric acid or hydrochloric acid.
Under the preferable case, the mother liquor that described silicon source part is produced when deriving from the preparation HTS, described reaction mixture also contains the silicon source that adds.Under above-mentioned preferable case, can more easily adjust each components in proportions in the reaction mixture, can obtain ZSM-5 molecular sieve of the present invention easilier.In the described reaction mixture, the silicon source of the mother liquor that is produced when deriving from the preparation HTS can change in the larger context with the content that adds the silicon source, under the preferable case, with SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, and the content in the silicon source of the mother liquor that is produced when deriving from the preparation HTS is 1-50 weight %, and the content that adds the silicon source is 50-99 weight %.
In reaction mixture of the present invention, when also needing to add the silicon source the silicon source in mother liquor, it can be silicon known in those skilled in the art source that the present invention should add the silicon source, is preferably in water glass, silicon sol, silica gel and the alumino silica gel one or more.Aluminium of the present invention source and alkali are conventionally known to one of skill in the art, and for example described aluminium source can be one or more in Tai-Ace S 150, sodium aluminate and the alumino silica gel; Described alkali can be one or more in sodium hydroxide, potassium hydroxide, ammonium hydroxide and the alkaline template, and described alkaline template is the basic cpd in the organic formwork agent.
Reaction mixture of the present invention can also contain organic formwork agent Q, and the consumption of described organic formwork agent makes Q/SiO in the described reaction mixture
2Mol ratio be 0.03-0.5, described organic formwork agent Q can be that to have quaternary ammonium salt that carbonatoms is the alkyl of 1-4, have carbonatoms be that the quaternary ammonium hydroxide and the general formula of the alkyl of 1-4 is R (NH
2)
nAlkylamine in one or more, wherein R be carbonatoms be 1-6 alkyl or the industry alkyl, n is 1 or 2.
Under the preferable case, described reaction mixture also comprises the seed molecule sieve.The kind of described seed molecule sieve is conventionally known to one of skill in the art.For example, described seed molecule sieve can be Y zeolite and/or ZSM-5 molecular sieve, with SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is below the 5 weight %.
The condition of hydrothermal crystallizing of the present invention generally includes: crystallization temperature is 110-220 ℃, and crystallization time is 6 hours to 10 days.Under the preferable case, described crystallization temperature is 130-220 ℃, and crystallization time is 1-6 days.Further under the preferable case, before carrying out described hydrothermal crystallizing, earlier reaction mixture is carried out ageing, described aged temperature is 20-110 ℃, is preferably 30-100 ℃, and the described aged time is 4-48 hour, is preferably 8-24 hour.
In addition, need to prove that when relating to consumption, silicon of the present invention source is all with SiO
2Meter, described aluminium source is all with Al
2O
3Meter, described alkali is all with Na
2The O meter.
Further specify method of the present invention below by embodiment.
Below among each embodiment, the relative crystallinity of product is that X-ray diffraction separately (XRD) spectrogram with this product and standard specimen is that the ratio of the peak height sum of five the XRD diffraction peaks (being commonly called as Five Fingers Peak) between 22.5-25.0 ° is represented at 2 θ angles.The sample of standard specimen wherein for making as follows is defined as 100% with its degree of crystallinity.
The preparation of standard specimen: 0.56 gram NaOH (chemical pure) is dissolved in the 28 gram deionized waters, under agitation adds 1.34 gram Al
2(SO
4)
318H
2O and 1.46 gram n-Butyl Amine 99s (chemical pure) add 12 gram 40-120 purpose silica gel (Haiyang Chemical Plant, Qingdao's product) again, obtain mixture.This mixture is placed the stainless steel sealed reactor,, obtains product after the cooling 170 ℃ of following hydrothermal crystallizings 24 hours, with this product after filtration, washing, drying obtain standard specimen.The XRD crystalline phase figure of this standard specimen shows that this standard specimen is the ZSM-5 molecular sieve as shown in Figure 1.
The mother liquor that is produced during the described preparation HTS used in the various embodiments of the present invention in addition, is the mother liquor that following method obtains:
Method according to the embodiment 1 of US 4410501 is prepared: under whipped state, 15 gram tetraethyl titanates are added in the 455 gram tetraethyl orthosilicates, and then be added dropwise to 800 the gram 25 weight % the tetrapropyl oxyammonia aqueous solution, stirred 1 hour, being heated to 80-90 ℃ then kept 5 hours, adding deionized water then makes cumulative volume reach 1.5 liters, this liquid is transferred in the autoclave, under agitation 175 ℃ of following crystallization 10 days, be cooled to room temperature, filter, promptly obtain needed HTS, the filtrate that filtration is obtained is used for the synthetic of following each embodiment ZSM-5 molecular sieve as mother liquor.The analysis showed that (Chen Biyou compiles, factory's analytical chemistry handbook, and National Defense Industry Press, 1992:261), SiO in this mother liquor
2Content is 5 weight %, and the pH value is 13.
Embodiment 1
Present embodiment illustrates the synthetic method of ZSM-5 molecular sieve of the present invention.
Under agitation to the 11.3 water glass solution (Na that contain 3.5 weight % that restrain
2O, 10 weight %SiO
2) the middle 5 restraints mother liquor of HTS fully that adds, the aluminum sulfate aqueous solutions that add 1.3 grams again (contain 2.5 weight %Al
2O
3), re-use 20% sulphuric acid soln and adjust pH value to 11.5, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=72, Na
2O/SiO
2=0.27, H
2O/SiO
2=36.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 18 weight % from the content in the silicon source of mother liquor, and the content that adds the silicon source is 82 weight %.
Then with this reaction mixture in autoclave 180 ℃ of following hydrothermal crystallizings 20 hours, crystallization is finished postcooling to room temperature, filters, and the filter cake that obtains after filtering 120 ℃ of bakings 2 hours down, is obtained product.The XRD crystalline phase figure and the described standard specimen of this product are similar, show that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 101%.
Embodiment 2
Present embodiment illustrates the synthetic method of ZSM-5 molecular sieve of the present invention.
Under agitation (contain 30 weight %SiO to 3.2 gram silicon sol
2) in add 0.13 gram sodium hydroxide and 10 and restrain the mother liquor that is equipped with HTS, the aluminum sulfate aqueous solutions that add 1.3 grams again (contain 2.5 weight %Al
2O
3), obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=50, Na
2O/SiO
2=0.1, H
2O/SiO
2=43.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 34 weight % from the content in the silicon source of mother liquor, and the content that adds the silicon source is 66 weight %.
Then with this reaction mixture in autoclave 180 ℃ of following hydrothermal crystallizings 30 hours, crystallization is finished postcooling to room temperature, filters, and the filter cake that obtains after filtering 120 ℃ of bakings 2 hours down, is obtained product.The XRD crystalline phase figure and the described standard specimen of this product are similar, show that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 110%.
Embodiment 3
Present embodiment illustrates the synthetic method of ZSM-5 molecular sieve of the present invention.
0.88 gram NaOH is dissolved in 36 restrains in the mother liquor that is equipped with HTS, under agitation add 0.45 gram Al
2(SO
4)
318H
2O and 2.19 gram n-Butyl Amine 99s add 11.5 gram silica gel again, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=45, Na
2O/SiO
2=0.05, n-Butyl Amine 99/SiO
2=0.16, H
2O/SiO
2=8.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 13 weight % from the content in the silicon source of mother liquor, and the content that adds the silicon source is 87 weight %.
Then with this reaction mixture in the stainless steel sealed reactor 150 ℃ of following hydrothermal crystallizings 25 hours, crystallization is finished postcooling to room temperature, filters, the filter cake deionized water wash with obtaining after filtering toasted 2 hours down at 120 ℃, obtained product.The XRD crystalline phase figure and the described standard specimen of this product are similar, show that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 97%.
Embodiment 4
Present embodiment illustrates the synthetic method of ZSM-5 molecular sieve of the present invention.
With 0.48 gram NaOH, 12 gram alumino silica gel (Qingdao silica gel factory, mol ratio SiO
2/ Al
2O
3=300) join 22 the gram the preparation HTS mother liquor and in, stir, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=340, Na
2O/SiO
2=0.03, H
2O/SiO
2=6.With SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, is 8 weight % from the content in the silicon source of mother liquor, and the content that adds the silicon source is 92 weight %.
Then with this reaction mixture in the stainless steel sealed reactor 170 ℃ of following hydrothermal crystallizings 20 hours, crystallization is finished postcooling to room temperature, filters, the filter cake deionized water wash with obtaining after filtering toasted 2 hours down at 120 ℃, obtained product.The XRD crystalline phase figure and the described standard specimen of this product are similar, show that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 102%.
Embodiment 5
Present embodiment illustrates the synthetic method of ZSM-5 molecular sieve of the present invention.
0.88 gram NaOH is dissolved in 10 restrains in the mother liquor that is equipped with HTS, under agitation add 0.45 gram Al
2(SO
4)
318H
2O and 2.19 gram n-Butyl Amine 99s, adding has the seed molecule of 0.25 gram sieve (ZSM-5 molecular sieve, the production of Shandong catalyst plant, mol ratio SiO
2/ Al
2O
3=35) add 11.5 gram silica gel again, obtain reaction mixture.In this reaction mixture, mol ratio SiO
2/ Al
2O
3=45, Na
2O/SiO
2=0.05, n-Butyl Amine 99/SiO
2=0.15, H
2O/SiO
2=8.With SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is 2 weight %.With silicon source weight total in the reaction mixture is benchmark, is 5 weight % from the content in the silicon source of mother liquor, and the content that adds the silicon source is 95 weight %.
Then with this reaction mixture in the stainless steel sealed reactor 150 ℃ of following hydrothermal crystallizings 24 hours, crystallization is finished postcooling to room temperature, filters, the filter cake deionized water wash with obtaining after filtering toasted 2 hours down at 120 ℃, obtained product.The XRD crystalline phase figure and the described standard specimen of this product are similar, show that this product is the ZSM-5 molecular sieve, and degree of crystallinity is 98%.
Claims (11)
1. the synthetic method of a ZSM-5 molecular sieve, this method comprise mixes silicon source, aluminium source, alkali and water, obtains reaction mixture, with this reaction mixture hydrothermal crystallizing, it is characterized in that, and in the described reaction mixture, SiO
2/ Al
2O
3Mol ratio is 20-1000, Na
2O/SiO
2Mol ratio is 0.03-0.5, H
2O/SiO
2Mol ratio is 5-20, described silicon source, alkali and water partly or entirely derive from the mother liquor that preparation is produced during HTS.
2. method according to claim 1, wherein, the mother liquor that described silicon source part is produced when deriving from the preparation HTS, described reaction mixture also contains the silicon source that adds.
3. method according to claim 2, wherein, with SiO
2Meter is a benchmark with silicon source weight total in the reaction mixture, and the content in the silicon source of the mother liquor that is produced when deriving from the preparation HTS is 1-50 weight %, and the content that adds the silicon source is 50-99 weight %.
4. according to claim 2 or 3 described methods, wherein, the described silicon source that adds is in water glass, silicon sol, silica gel and the alumino silica gel one or more.
5. according to claim 1,2 or 3 described methods, wherein, described reaction mixture also contains organic formwork agent, and the consumption of described organic formwork agent makes organic formwork agent/SiO in the described reaction mixture
2Mol ratio be 0.03-0.5.
6. method according to claim 5, wherein, described organic formwork agent is that to have quaternary ammonium salt that carbonatoms is the alkyl of 1-4, have carbonatoms be that the quaternary ammonium hydroxide and the general formula of the alkyl of 1-4 is R (NH
2)
nAlkylamine in one or more, wherein R is that carbonatoms is alkyl or the alkylidene group of 1-6, n is 1 or 2.
7. according to claim 1,2 or 3 described methods, wherein, described reaction mixture also contains the seed molecule sieve, with SiO
2Meter is a benchmark with the gross weight in the silicon source in the reaction mixture, and the content of described seed molecule sieve is below the 5 weight %.
8. method according to claim 7, wherein, described seed molecule sieve is Y zeolite and/or ZSM-5 molecular sieve.
9. method according to claim 1, wherein, the condition of described hydrothermal crystallizing comprises: crystallization temperature is 110-220 ℃, crystallization time is 6 hours to 10 days.
10. method according to claim 1, wherein, described aluminium source is one or more in Tai-Ace S 150, sodium aluminate and the alumino silica gel.
11. method according to claim 1, wherein, described alkali is one or more in sodium hydroxide, potassium hydroxide, ammonium hydroxide and the alkaline template.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372283B (en) * | 2010-08-23 | 2013-07-31 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and its preparation method |
| CN102942193B (en) * | 2012-11-26 | 2014-12-24 | 中国寰球工程公司辽宁分公司 | Method for synthesizing novel thin layer ZSM-5 zeolite with boron-containing framework |
| CN103936026A (en) * | 2014-04-03 | 2014-07-23 | 南京工业大学 | Method for synthesizing ZSM-5 molecular sieve |
| CN104003415B (en) * | 2014-05-27 | 2016-01-13 | 复旦大学 | A kind of preparation method of nano-sized ZSM-5 zeolite of high-crystallinity |
| CN112694099A (en) * | 2019-10-21 | 2021-04-23 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
| CN114515595B (en) * | 2020-11-19 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by cracking carbon tetraolefin containing titanium-silicon ordered pore material, preparation method thereof and application thereof in catalytic cracking reaction |
| CN112624144B (en) * | 2020-12-25 | 2024-03-12 | 南开大学 | Preparation method of heteroatom MFI molecular sieve nanosheets |
| CN113830788A (en) * | 2021-10-13 | 2021-12-24 | 中国科学院过程工程研究所 | ZSM-5 molecular sieve and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1056818C (en) * | 1997-01-10 | 2000-09-27 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1257840C (en) * | 2003-03-11 | 2006-05-31 | 中国石油化工股份有限公司 | ZSM-5 structure zeolite, preparation and use thereof |
-
2007
- 2007-12-25 CN CN200710304108XA patent/CN101468805B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1056818C (en) * | 1997-01-10 | 2000-09-27 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1257840C (en) * | 2003-03-11 | 2006-05-31 | 中国石油化工股份有限公司 | ZSM-5 structure zeolite, preparation and use thereof |
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