CN102897790A - Synthesis method for ZSM-5 molecular sieve - Google Patents
Synthesis method for ZSM-5 molecular sieve Download PDFInfo
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- CN102897790A CN102897790A CN2011102145016A CN201110214501A CN102897790A CN 102897790 A CN102897790 A CN 102897790A CN 2011102145016 A CN2011102145016 A CN 2011102145016A CN 201110214501 A CN201110214501 A CN 201110214501A CN 102897790 A CN102897790 A CN 102897790A
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Abstract
The present invention discloses a synthesis method for a ZSM-5 molecular sieve, comprising the steps of: (1) mixing a quaternary ammonium base, an fatty amine, and an aluminum source to obtain a mixture, wherein the mole ratio of the organic templating agent and Al2O3 in the aluminum source is 0.2-40:1, and processing the mixture in a closed reactor at 50 DEG C to 190 DEG C for 0.1 to 5 hours then cooling to obtain an intermediate product; (2) mixing the intermediate product obtained in step (1) with a silicon source and water uniformly; (3) placing the mixture obtained in the step (2) in a closed reactor and processing for 10 -120 hours at 100-200 DEG C, and obtaining a hydrogen-type ZSM-5 molecular sieve product by recovering. The method uses a synthesis route different from a sodium free system in the prior art, so that costly silica-alumina gel as the silicon source and the aluminum source can abandoned, and the hydrogen-type ZSM-5 can still be obtained, reducing the cost of synthesis. Additionally, the primary grain of the ZSM-5 molecular sieve synthesized by the method is between 0.05 [mu]m and 0.5[mu]m.
Description
Technical field
The invention relates to a kind of synthetic method of ZSM-5 molecular sieve, more specifically say the synthetic method about a kind of ZSM-5 molecular sieve without the sodium system.
Background technology
ZSM-5 molecular sieve is the high silicon mesoporous molecular sieve with MFI structure, and it has unique pore passage structure, is widely used in the petrochemical complex significant element such as catalytic cracking, aromizing, alkylation.
The synthetic system of ZSM-5 molecular sieve adopts mineral alkali (such as sodium hydroxide) to form the suitable required alkaline environment of Crystallization of Zeolite usually, and synthetic molecular sieve is sodium type ZSM-5, must just can be transformed into the hydrogen type molecular sieve catalyzer through ion-exchange.Ion-exchange process produces a large amount of ammonia-nitrogen sewages or acid-bearing wastewater, and manufacturing enterprise is caused very large environmental protection pressure.
The disclosed synthetic method of CN1935652A, be by directed agents solution, adopt liquid silicon source and liquid aluminium source hydrothermal crystallizing to make ZSM-5 molecular sieve, directed agents solution is made the first organic bases template with 4-propyl bromide or TPAOH, reaction mixture is made the second organic bases template with ring molecule amine-hexamethylene imine or piperidines or both mixtures, this synthetic method saves ion-exchange process, does not contain the ammonium nitrogen wastewater discharging.
CN1715186A discloses a kind of preparation method of small crystal grain ZSM-5 zeolite, is that the aqueous mixture with alumino silica gel particle and organic formwork agent carries out hydrothermal crystallizing.The method is avoided using the raw material that contains sodium ion in synthetic system, thereby has reduced ammonium exchange, filtration, a series of processes of roasting, has improved the yield of zeolite product, has simplified Production Flow Chart.This preparation method adopts the solid silicon aluminium glue to do raw material, and single-autoclave yield rate is high, but the cost of alumino silica gel is higher, is unfavorable for large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide and a kind ofly carry out low cost, single-autoclave yield rate ZSM-5 molecular sieve synthetic method high, simple flow with solid silicon source.
The invention provides the synthetic method of ZSM-5 molecular sieve, may further comprise the steps:
(1) be that 4～10: 1 organic formwork agent mixes the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source with quaternary ammonium hydroxide and the mol ratio of aliphatic amide
2O
3The mole proportioning be 0.2～40: 1, with mixture in closed reactor in 50～190 ℃ lower process 0.1～5 hour after cooling, obtain intermediate product;
(2) intermediate product of step (1) and silicon source and water are mixed, in the mixture in mole SiO
2/ Al
2O
3=20～300, H
2O/SiO
2=6～10;
(3) mixture with step (2) places 100～200 ℃ of lower processing 10～120 hours of closed reactor, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
Synthetic method provided by the invention, it is a kind of method without the synthetic Hydrogen ZSM-5 molecular sieve of sodium system, reduced and existing contained the sodium technical system and obtain the required ammonium exchange of Hydrogen ZSM-5 molecular sieve, filtration, a series of processes of roasting, but with without the raw material of sodium ion as synthesis material, allow first the mixture of aluminium source and template experience the hydrothermal treatment consists process, again with silicon source mixture process; Adopted and had now without the different synthesis route of sodium technical system, thereby can abandon expensive alumino silica gel as silicon source and aluminium source, but still can obtain the Hydrogen ZSM-5 molecular sieve, reduced synthetic cost.
Synthetic method provided by the invention can obtain SiO
2/ Al
2O
3The molecular sieve of mol ratio 15～280, wherein, relative crystallinity is at least 90%, and the elementary crystal grain of molecular sieve is at 0.05～0.5 μ m.
Synthetic method provided by the invention behind the Crystallization of Zeolite, is filtered the mother liquor that obtains and can also be continued to be applied in the preparation of molecular sieve, has both further reduced the Zeolite synthesis cost, also reduces pollution emissions simultaneously.
Embodiment
The invention provides the synthetic method of ZSM-5 molecular sieve, may further comprise the steps:
(1) be that 4～10: 1 organic formwork agent mixes the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source with quaternary ammonium hydroxide and the mol ratio of aliphatic amide
2O
3The mole proportioning be 0.2～40: 1, with mixture in closed reactor in 50～190 ℃ lower process 0.1～5 hour after cooling, obtain intermediate product;
(2) intermediate product of step (1) and silicon source and water are mixed, in the mixture in mole SiO
2/ Al
2O
3=20～300, H
2O/SiO
2=6～10;
(3) mixture with step (2) places 100～200 ℃ of lower processing 10～120 hours of closed reactor, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
Method provided by the invention, said organic formwork agent is selected from the mixture of quaternary ammonium hydroxide and aliphatic amide in the step (1), and the mol ratio of quaternary ammonium hydroxide and aliphatic amide is 4～10: 1, and preferred molar ratio is 6～9: 1.Said quaternary ammonium hydroxide is selected from one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, the TPAOH; Said aliphatic amide is selected from one or more in n-Butyl Amine 99, ethamine, the propylamine.In some preferred implementations, the composite type of quaternary ammonium hydroxide and aliphatic amide can be tetramethylammonium hydroxide aqueous solution and n-Butyl Amine 99 or tetraethyl ammonium hydroxide and n-Butyl Amine 99, or TPAOH and propylamine or n-Butyl Amine 99, etc., wherein in the most preferred scheme, composite type is the mixture of TPAOH and propylamine.Said aluminium source can be selected from one or more in pseudo-boehmite, aluminum oxide, the aluminium hydroxide.Al in the said mixture in organic formwork agent and the aluminium source
2O
3The mole proportioning be 0.2～40: 1, preferred 2～20: 1.The mole number of organic formwork agent is the total amount of quaternary ammonium hydroxide mole number and aliphatic amide mole number.
Method provided by the invention, said silicon source can be selected from silica gel and/or white carbon black in the step (2), the intermediate product of said step (2) and silicon source and water mix, in the mixture in mole, SiO
2/ Al
2O
3Be preferably 40～150, H
2O/SiO
2Be preferably 6～8.
Because in the said organic formwork agent of step (1), such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, ethamine etc. is that the aqueous solution with different percentage compositions exists; Also have not moisture, itself be exactly the organic formwork agent that liquid form exists, such as n-Butyl Amine 99 and propylamine etc., therefore, said water might be to be introduced by the aqueous solution of the organic formwork agent in the step (1) in the middle mixture of step (2), also might be in the situation that moisture deficit, in step (2), add in addition, in principle as long as mixture satisfies H in the step (2)
2O/SiO
2=6～10, preferred 6～8 requirement gets final product.
Method provided by the invention, said mixture in the step (3), in closed reactor, preferably 145～190 ℃, more preferably 170～190 ℃ lower processed more preferably 15～72 hours 15～100 hours.
In the method provided by the invention, the said recovery of step (3) refers to that product that processing is obtained is through the process of filtration, washing, drying and the roasting of routine.Drying means and condition are usual drying means and condition, for example 100～120 ℃ of dryings 4～24 hours in baking oven.Roasting method and condition are conventional method and the condition that the molecular sieve activation is adopted, for example roasting in retort furnace, and maturing temperature is 530～550 ℃, roasting time is 1～5 hour.
In the preferred embodiment in method provided by the invention, may further comprise the steps:
(1) be that 6～9: 1 organic formwork agent mixes the Al in the mixture in organic formwork agent and the aluminium source with one or more aluminium sources in being selected from pseudo-boehmite, aluminium hydroxide and aluminum oxide with the mol ratio of TPAOH and propylamine
2O
3The mole proportioning be 2～20: 1, with mixture in closed reactor in 80～180 ℃ lower process 0.1～5 hour after cooling, obtain intermediate product;
(2) intermediate product of step (1) and silica gel and water are mixed, in the mixture in mole SiO
2/ Al
2O
3=20～300, H
2O/SiO
2=6～8;
(3) mixture with step (2) places 110～190 ℃ of lower processing 10～120 hours of closed reactor, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
The invention will be further described below by embodiment, but content not thereby limiting the invention.
In an embodiment, the chemical constitution of molecular sieve is measured by x-ray fluorescence method.
Described relative crystallinity is that the ratio with the peak area sum of five characteristic diffraction peaks of 2 θ between 22.5～25.0 ° of X-ray diffraction (XRD) spectrogram of products therefrom and ZSM-5 molecular sieve standard specimen represents with percentage ratio.
Adopting the synthetic ZSM-5 molecular sieve of method of embodiment 1 among the CN1056818C is standard specimen, and its degree of crystallinity is decided to be 100%.
XRD measures at SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep velocity is 2 °/minute.
The grain size of molecular sieve adopts scanning electronic microscope to measure.
Embodiment 1～4 explanation synthetic method provided by the invention.
Embodiment 1
Take by weighing 2.87 gram aluminium hydroxide (Beijing Chemical Plant, analytical pure, Al
2O
3Content 35%), (the good friend in Beijing contains the new technology development center with itself and 50.25g tetramethylammonium hydroxide aqueous solution, analytical pure, TMAOH content 10%) and 1.02g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixes, mixture mol ratio TMAOH/ n-Butyl Amine 99=4, organic formwork agent/Al
2O
3=7.Be placed in the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 150 ℃ of reactions after 3 hours, afterwards, with itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO
2Content 98.4%) and 23.76g water mix mixture mol ratio SiO
2/ Al
2O
3=50, H
2O/SiO
2=8.Mixture carried out hydrothermal crystallizing 75 hours in 120 ℃ in autoclave.After the crystallization molecular sieve after filtration, after the washing in 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 3 hours obtain product Hydrogen ZSM-5 molecular sieve S-1.
The degree of crystallinity 90% of molecular sieve S-1, silica alumina ratio 48.The elementary grain size of S-1 is 400～500nm.
Embodiment 2
Take by weighing 0.33 gram pseudo-boehmite (Chang Ling catalyst plant, Al
2O
3Content 75%), with itself and the 11.64g tetraethyl ammonium hydroxide aqueous solution (Shanghai immortality chemical reagent work, analytical pure, TEAOH content 40%) and 0.39g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixes, mixture mol ratio TEAOH/ n-Butyl Amine 99=6, organic formwork agent/Al
2O
3=15.Be placed in the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 150 ℃ of reactions after 2 hours, afterwards, with itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO
2Content 98.4%) and 54.92g water mix mixture mol ratio SiO
2/ Al
2O
3=200, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 40 hours in 130 ℃ in autoclave.After the crystallization molecular sieve after filtration, after the washing in 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 3 hours obtain product Hydrogen ZSM-5 molecular sieve S-2.
The degree of crystallinity 91% of molecular sieve S-2, silica alumina ratio 183.The elementary grain size of S-2 is 100～450nm.
Embodiment 3
Take by weighing 0.64 gram aluminum oxide (Chang Ling catalyst plant, Al
2O
3Content 98%), (the good friend in Beijing contains the new technology development center with itself and the 36.38g TPAOH aqueous solution, analytical pure, TPAOH content 25%) and 0.27g propylamine (Chemical Reagent Co., Ltd., Sinopharm Group, content 98.5%,) mix mixture mol ratio TPAOH/ propylamine=10, organic formwork agent/Al
2O
3=8.Be placed in the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 150 ℃ of reactions after 4 hours, afterwards, with itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO
2Content 98.4%) and 34.7g water mix mixture mol ratio SiO
2/ Al
2O
3=80, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 20 hours in 175 ℃ in autoclave.After the crystallization molecular sieve after filtration, after the washing in 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 3 hours obtain product Hydrogen ZSM-5 molecular sieve S-3.
The degree of crystallinity 98% of molecular sieve S-3, silica alumina ratio 77.The elementary grain size of S-3 is 60～100nm.
Embodiment 4
Take by weighing 1.29 gram aluminum oxide (Chang Ling catalyst plant, Al
2O
3Content 98%), (the good friend in Beijing contains the new technology development center with itself and the 27.18g TPAOH aqueous solution, analytical pure, TPAOH content 25%) and 0.28g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixes, mixture mol ratio TPAOH/ n-Butyl Amine 99=9, organic formwork agent/Al
2O
3=3.Be placed in the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 150 ℃ of reactions after 4 hours, afterwards, with itself and 30g white carbon black (Shenyang Chemical Co., Ltd., SiO
2Content 99%) and 41.99g water mix mixture mol ratio SiO
2/ Al
2O
3=40, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 20 hours in 175 ℃ in autoclave.After the crystallization molecular sieve after filtration, after the washing in 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 3 hours obtain product Hydrogen ZSM-5 molecular sieve S-4.
The degree of crystallinity 91% of molecular sieve S-4, silica alumina ratio 35.The elementary grain size of S-4 is 60～300nm.
Claims (9)
1. the synthetic method of a ZSM-5 molecular sieve may further comprise the steps:
(1) be that 4～10: 1 organic formwork agent mixes the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source with quaternary ammonium hydroxide and the mol ratio of aliphatic amide
2O
3The mole proportioning be 0.2～40: 1, with mixture in closed reactor in 50～190 ℃ lower process 0.1～5 hour after cooling, obtain intermediate product;
(2) intermediate product of step (1) and silicon source and water are mixed, in the mixture in mole SiO
2/ Al
2O
3=20～300, H
2O/SiO
2=6～10;
(3) mixture with step (2) places 100～200 ℃ of lower processing 10～120 hours of closed reactor, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
2. according to the synthetic method of claim 1, wherein, the said organic formwork agent of step (1) is selected from the mixture of quaternary ammonium hydroxide and aliphatic amide, and the mol ratio of quaternary ammonium hydroxide and aliphatic amide is 6～9: 1.
3. according to the synthetic method of claim 1 or 2, wherein, said quaternary ammonium hydroxide is selected from one or more in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, the TPAOH; Said aliphatic amide is selected from one or more in n-Butyl Amine 99, ethamine, the propylamine.
4. according to the synthetic method of claim 1, wherein, said organic formwork agent is tetramethylammonium hydroxide aqueous solution and n-Butyl Amine 99 or is tetraethyl ammonium hydroxide and n-Butyl Amine 99, perhaps is TPAOH and the third ammonium, perhaps is TPAOH and n-Butyl Amine 99.
5. according to the synthetic method of claim 1, wherein, the said aluminium of step (1) source is selected from one or more in pseudo-boehmite, aluminum oxide, the aluminium hydroxide.
6. according to the synthetic method of claim 1, wherein, the Al in the said mixture of step (1) in organic formwork agent and the aluminium source
2O
3The mole proportioning be 1～30: 1.
7. according to the synthetic method of claim 1, wherein, the said silicon of step (2) source is selected from silica gel and/or white carbon black.
8. according to the synthetic method of claim 1, wherein, in the mixture of step (2) in mole, SiO
2/ Al
2O
3=40～150, H
2O/SiO
2=6～8.
9. according to the synthetic method of claim 1, may further comprise the steps:
(1) be that 6～9: 1 organic formwork agent mixes the Al in the mixture in organic formwork agent and the aluminium source with one or more aluminium sources in being selected from pseudo-boehmite, aluminium hydroxide and aluminum oxide with the mol ratio of TPAOH and propylamine
2O
3The mole proportioning be 2～20: 1, with mixture in closed reactor in 80～180 ℃ lower process 0.1～5 hour after cooling, obtain intermediate product;
(2) intermediate product of step (1) and silica gel and water are mixed, in the mixture in mole SiO
2/ Al
2O
3=20～300, H
2O/SiO
2=6～8;
(3) mixture with step (2) places 110～190 ℃ of lower processing 10～120 hours of closed reactor, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| CN109694085A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet |
| CN114426287A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0042225B1 (en) * | 1980-06-12 | 1984-02-01 | Imperial Chemical Industries Plc | Zeolite synthesis |
| US4526767A (en) * | 1983-01-11 | 1985-07-02 | Coal Industry (Patents) Ltd. | Process for the production of ZSM-5 zeolite |
| CN101624192A (en) * | 2009-08-10 | 2010-01-13 | 大唐国际化工技术研究院有限公司 | ZSM-5 type molecular sieve for catalyst for reaction for preparing propylene from methanol and/or dimethyl ether |
-
2011
- 2011-07-29 CN CN201110214501.6A patent/CN102897790B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0042225B1 (en) * | 1980-06-12 | 1984-02-01 | Imperial Chemical Industries Plc | Zeolite synthesis |
| US4526767A (en) * | 1983-01-11 | 1985-07-02 | Coal Industry (Patents) Ltd. | Process for the production of ZSM-5 zeolite |
| CN101624192A (en) * | 2009-08-10 | 2010-01-13 | 大唐国际化工技术研究院有限公司 | ZSM-5 type molecular sieve for catalyst for reaction for preparing propylene from methanol and/or dimethyl ether |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| CN109694085A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet |
| CN114426287A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
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