CN102897791B - Synthesis method for ZSM-5 molecular sieve - Google Patents
Synthesis method for ZSM-5 molecular sieve Download PDFInfo
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- CN102897791B CN102897791B CN201110214507.3A CN201110214507A CN102897791B CN 102897791 B CN102897791 B CN 102897791B CN 201110214507 A CN201110214507 A CN 201110214507A CN 102897791 B CN102897791 B CN 102897791B
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Abstract
The present invention discloses a synthesis method for a ZSM-5 molecular sieve, comprising the steps of: (1) mixing an organic templating agent and an aluminum source, 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, wherein tetrapropylammonium hydroxide is account for 30-80 mole % of the organic templating agent; (2) mixing the intermediate product obtained in the step (1) with a silicon source and water uniformly, SiO2/Al2O3 = 20-300 and H2O/SiO2 = 6-10 in the mixture on a molar basis; (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 recovering a hydrogen-type ZSM-5 molecular sieve product. The method uses a synthesis route different from a sodium free system in the prior art, so 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. The primary grain of the ZSM-5 molecular sieve obtained is between 0.05 [mu]m and 0.5[mu]m, and the relative crystallinity is at least 95%.
Description
Technical field
The invention relates to a kind of preparation method of ZSM-5 molecular sieve, is more particularly the preparation method about a kind of ZSM-5 molecular sieve without 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 (as sodium hydroxide) to form alkaline environment needed for applicable Crystallization of Zeolite usually, and the molecular sieve of synthesis is sodium form ZSM-5, has to pass through ion-exchange and just can be transformed into hydrogen type molecular sieve catalyzer.Ion-exchange process produces a large amount of ammonia-nitrogen sewage or acid-bearing wastewater, causes very large environmental protection pressure to manufacturing enterprise.
Synthetic method disclosed in CN1935652A, be by directing agent solution, adopt liquid silicon source and liquid aluminium source hydrothermal crystallizing to obtain ZSM-5 molecular sieve, directing agent solution makes the first organic bases template with 4-propyl bromide or TPAOH, reaction mixture makes the second organic bases template with ring molecule amine-hexamethylene imine or piperidines or both mixtures, this synthetic method saves ion-exchange process, not containing ammonium nitrogen wastewater discharge.
CN1715186A discloses a kind of preparation method of small crystal grain ZSM-5 zeolite, is the aqueous mixture of alumino silica gel particle and organic formwork agent is carried out hydrothermal crystallizing.The method is avoided using the raw material containing sodium ion in synthetic system, thus decreases ammonium exchange, filtration, a series of process of roasting, improves the yield of zeolite product, simplifies Production Flow Chart.This preparation method adopts 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 object of this invention is to provide a kind of low cost, single-autoclave yield rate high, the ZSM-5 molecular sieve preparation method of simple flow.
The invention provides a kind of preparation method of ZSM-5 molecular sieve, comprise the following steps:
(1) organic formwork agent is mixed with aluminium source, the Al in mixture in organic formwork agent and aluminium source
2o
3mol ratio be 0.2 ~ 40: 1, mixture is processed cooling after 0.1 ~ 5 hour in closed reactor at 50 ~ 190 DEG C, and obtain intermediate product, wherein, in said organic formwork agent, TPAOH accounts for molar percentage 30 ~ 80%;
(2) intermediate product of step (1) is mixed with silicon source and water, in a mole SiO in mixture
2/ Al
2o
3=20 ~ 300, H
2o/SiO
2=6 ~ 10;
(3) process 10 ~ 120 hours at the mixture of step (2) being placed in closed reactor 100 ~ 200 DEG C, and recovery obtains Hydrogen ZSM-5 molecular sieve product
Preparation method provided by the invention, decrease and existingly prepare a series of process such as ammonium exchange, filtration, roasting required for Hydrogen ZSM-5 molecular sieve containing sodium technical system, but using the raw material without sodium ion as raw materials, first allow the mixture of aluminium source and template experience hydrothermal treatment process, then with silicon source mixture process.Have employed and the existing preparation were established different without sodium technical system, thus the alumino silica gel can abandoning high cost is as silicon source and aluminium source, but still can obtain Hydrogen ZSM-5 molecular sieve, reduce preparation cost.In addition, the ZSM-5 molecular sieve that the inventive method prepares, its SiO
2/ Al
2o
3mol ratio 15 ~ 280, primary grains at 0.05 ~ 0.5 μm, relative crystallinity at least 95%.
Preparation method provided by the invention, after Crystallization of Zeolite, filters the mother liquor obtained and can also continue to be applied in the preparation of molecular sieve, both reduced Zeolite synthesis cost further, also reduce pollution emissions simultaneously.
Embodiment
The invention provides a kind of preparation method of ZSM-5 molecular sieve, comprise the following steps:
(1) organic formwork agent is mixed with aluminium source, the Al in mixture in organic formwork agent and aluminium source
2o
3mol ratio be 0.2 ~ 40: 1, mixture is processed cooling after 0.1 ~ 5 hour in closed reactor at 50 ~ 190 DEG C, obtains intermediate product, wherein, the molar percentage 30 ~ 80% of TPAOH in said organic formwork agent;
(2) intermediate product of step (1) is mixed with silicon source and water, in a mole SiO in mixture
2/ Al
2o
3=20 ~ 300, H
2o/SiO
2=6 ~ 10;
(3) process 10 ~ 120 hours at the mixture of step (2) being placed in closed reactor 100 ~ 200 DEG C, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
In method provided by the invention, in step (1), said organic formwork agent is selected from the mixture of TPAOH and other quaternary ammonium hydroxide or aliphatic amide, and wherein TPAOH accounts for 30-80% molar percentage, and preferably 50 ~ 80%.Other quaternary ammonium hydroxide said is selected from Tetramethylammonium hydroxide and/or tetraethyl ammonium hydroxide; It is several that said aliphatic amide is selected from one or more in n-Butyl Amine 99, ethamine and propylamine.In some preferred embodiments, organic formwork agent is selected from the mixture of TPAOH and n-Butyl Amine 99.
Said aluminium source can be selected from one or more in pseudo-boehmite, aluminum oxide, aluminium hydroxide.Al in said mixture in organic formwork agent and aluminium source
2o
3mol ratio be 0.2 ~ 40: 1, preferably 1 ~ 30: 1.
Method provided by the invention, in step (2), said silicon source can be selected from silica gel and/or white carbon black, wherein preferred silica gel.The product of said step (2) mixes with silicon source and water, in mixture in mole, SiO
2/ Al
2o
3be preferably 40 ~ 150, H
2o/SiO
2preferably 6 ~ 8.
Due in step (1) said organic formwork agent, such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, ethamine etc. exist with the aqueous solution of different percentage composition; Also organic formwork agent that is not moisture, inherently liquid form existence is had, such as n-Butyl Amine 99 and propylamine etc., therefore, in step (2), in mixture, said water is likely introduced by the aqueous solution of the organic formwork agent in step (1), also likely when moisture deficit, add in addition in step (2), as long as the middle mixture of step (2) meets H in principle
2o/SiO
2=6 ~ 10, preferably 6 ~ 8 requirement.
Method provided by the invention, said mixture in step (3), in closed reactor, preferably process 15 ~ 75 hours at 110 ~ 150 DEG C, more preferably 120 ~ 140 DEG C, more preferably 24 ~ 36 hours.
In method provided by the invention, step (3) said recovery refers to the process by processing the filtration through routine of the product that obtains, washing, drying and roasting.Drying means and condition are usual drying means and condition, such as 100 ~ 120 DEG C of dryings 4 ~ 24 hours in an oven.The conventional method that roasting method and condition adopt for molecular sieve activation and condition, such as roasting in retort furnace, maturing temperature is 530 ~ 550 DEG C, and roasting time is 1 ~ 5 hour.
Below by embodiment, the invention will be further described, 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 represents with percentage ratio with the ratio of 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.XRD measures on SIMENS D5005 type X-ray diffractometer, CuK α radiation, 44 kilovolts, and 40 milliamperes, sweep velocity is 2 °/minute.
The ZSM-5 molecular sieve adopting the method synthesis of embodiment 1 in CN1056818C is standard specimen, and its degree of crystallinity is decided to be 100%.
The grain size of molecular sieve adopts scanning electronic microscope to measure.
Embodiment 1 ~ 5 illustrates molecular sieve preparation method provided by the invention.
Embodiment 1
Take 2.87 grams of aluminium hydroxides (Beijing Chemical Plant, analytical pure, Al
2o
3content 35%), by itself and the 13.34g TPAOH aqueous solution, (the good friend in Beijing contains new technology development center, analytical pure, TPAOH content 25%) and 2.44g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixing, mixture mol ratio organic formwork agent/Al
2o
3=5.Be placed in the crystallizing kettle containing polytetrafluoro lining, be cooled to room temperature, afterwards, by itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO in 150 DEG C of reactions after 4 hours
2content 98.4%) and the mixing of 58.98g water, mixture mol ratio SiO
2/ Al
2o
3=50, H
2o/SiO
2=8.Mixture carries out hydrothermal crystallizing 24 hours in 140 DEG C in autoclave.After crystallization, molecular sieve after filtration, dry 4 hours in 120 DEG C after washing, and 550 DEG C of roastings 3 hours, obtain product Hydrogen ZSM-5 molecular sieve S-1.
The degree of crystallinity 95% of molecular sieve S-1, silica alumina ratio 48.S-1 primary grains size is 400 ~ 500nm.
Embodiment 2
Take 0.33 gram of pseudo-boehmite (Chang Ling catalyst plant, Al
2o
3content 75%), by itself and the 15.01g TPAOH aqueous solution, (the good friend in Beijing contains new technology development center, analytical pure, TPAOH content 25%) and 1.37g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixing, mixture mol ratio organic formwork agent/Al
2o
3=15.Be placed in the crystallizing kettle containing polytetrafluoro lining, be cooled to room temperature, afterwards, by itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO in 150 DEG C of reactions after 3 hours
2content 98.4%) and the mixing of 50.65g water, mixture mol ratio SiO
2/ Al
2o
3=200, H
2o/SiO
2=7.Mixture carries out hydrothermal crystallizing 30 hours in 130 DEG C in autoclave.After crystallization, molecular sieve after filtration, dry 4 hours in 120 DEG C after washing, and 550 DEG C of roastings 3 hours, obtain product Hydrogen ZSM-5 molecular sieve S-2.
The degree of crystallinity 97% of molecular sieve S-2, silica alumina ratio 183.S-2 primary grains size is 100 ~ 300nm.
Embodiment 3
Take 0.64 gram of aluminum oxide (Chang Ling catalyst plant, Al
2o
3content 98%), by itself and the 26.68g TPAOH aqueous solution, (the good friend in Beijing contains new technology development center, analytical pure, TPAOH content 25%) and 0.98g propylamine (Chemical Reagent Co., Ltd., Sinopharm Group, content 98.5%) mixing, mixture mol ratio organic formwork agent/Al
2o
3=8.Be placed in the crystallizing kettle containing polytetrafluoro lining, be cooled to room temperature, afterwards, by itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO in 150 DEG C of reactions after 2 hours
2content 98.4%) and the mixing of 59.69g water, mixture mol ratio SiO
2/ Al
2o
3=80, H
2o/SiO
2=9.Mixture carries out hydrothermal crystallizing 36 hours in 125 DEG C in autoclave.After crystallization, molecular sieve after filtration, dry 4 hours in 120 DEG C after washing, and 550 DEG C 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.S-3 primary grains size is 60 ~ 300nm.
Embodiment 4
Take 0.45 gram of pseudo-boehmite (Chang Ling catalyst plant, Al
2o
3content 75%), by itself and the 20.13g TPAOH aqueous solution, (the good friend in Beijing contains new technology development center, analytical pure, TPAOH content 25%) and 1.84g n-Butyl Amine 99 (Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure) mixing, mixture mol ratio organic formwork agent/Al
2o
3=15.Be placed in the crystallizing kettle containing polytetrafluoro lining, be cooled to room temperature, afterwards, by itself and 30g white carbon black (Shenyang Chemical Co., Ltd., SiO in 150 DEG C of reactions after 3 hours
2content 99%) and the mixing of 47.16g water, mixture mol ratio SiO
2/ Al
2o
3=150, H
2o/SiO
2=7.Mixture carries out hydrothermal crystallizing 24 hours in 130 DEG C in autoclave.After crystallization, molecular sieve after filtration, dry 4 hours in 120 DEG C after washing, and 550 DEG C of roastings 3 hours, obtain product Hydrogen ZSM-5 molecular sieve S-4.
The degree of crystallinity 95% of molecular sieve S-4, silica alumina ratio 133.S-4 primary grains size is 400 ~ 500nm.
Embodiment 5
Take 0.84 gram of pseudo-boehmite (Chang Ling catalyst plant, Al
2o
3content 75%), by itself and the 30.02g TPAOH aqueous solution, (the good friend in Beijing contains new technology development center, analytical pure, TPAOH content 25%) and the 13.58g tetraethyl ammonium hydroxide aqueous solution (Shanghai immortality chemical reagent work, analytical pure, TEAOH content 40%) mixing, mixture mol ratio organic formwork agent/Al
2o
3=12.Be placed in the crystallizing kettle containing polytetrafluoro lining, be cooled to room temperature, afterwards, by itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO in 150 DEG C of reactions after 2 hours
2content 98.4%) and the mixing of 39.27g water, mixture mol ratio SiO
2/ Al
2o
3=80, H
2o/SiO
2=7.Mixture carries out hydrothermal crystallizing 30 hours in 130 DEG C in autoclave.After crystallization, molecular sieve after filtration, dry 4 hours in 120 DEG C after washing, and 550 DEG C of roastings 3 hours, obtain product Hydrogen ZSM-5 molecular sieve S-5.
The degree of crystallinity 99% of molecular sieve S-5, silica alumina ratio 75.S-5 primary grains size is 50 ~ 150nm.
Claims (5)
1. a preparation method for ZSM-5 molecular sieve, comprises the following steps:
(1) organic formwork agent is mixed with aluminium source, the Al in mixture in organic formwork agent and aluminium source
2o
3mol ratio be 0.2 ~ 40: 1, cooling after mixture is processed 0.1 ~ 5 hour in closed reactor at 50 ~ 190 DEG C, obtain intermediate product, wherein, said organic formwork agent is selected from the mixture of TPAOH and other quaternary ammonium hydroxide or aliphatic amide, wherein TPAOH accounts for 30 ~ 80 % by mole, and other quaternary ammonium hydroxide is selected from Tetramethylammonium hydroxide and/or tetraethyl ammonium hydroxide; It is several that said aliphatic amide is selected from one or more in n-Butyl Amine 99, ethamine and propylamine, and said aluminium source is selected from one or more in pseudo-boehmite, aluminum oxide, aluminium hydroxide;
(2) intermediate product of step (1) is mixed with silicon source and water, in a mole SiO in mixture
2/ Al
2o
3=20 ~ 300, H
2o/SiO
2=6 ~ 10;
(3) process 10 ~ 120 hours at the mixture of step (2) being placed in closed reactor 100 ~ 200 DEG C, and recovery obtains Hydrogen ZSM-5 molecular sieve product.
2. according to the preparation method of claim 1, wherein, in step (1) said organic formwork agent, TPAOH accounts for 50 ~ 80 % by mole.
3. the Al according to the preparation method of claim 1, wherein, in step (1) said mixture in organic formwork agent and aluminium source
2o
3mol ratio be 1 ~ 30: 1.
4. according to the preparation method of claim 1, wherein, the said silicon source of step (2) is silica gel.
5. according to the preparation method of claim 1, wherein, in step (2) said mixture in mole, SiO
2/ Al
2o
3be 40 ~ 150, H
2o/SiO
2be 6 ~ 8.
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| JP2016512788A (en) * | 2013-03-15 | 2016-05-09 | ビーピー・コーポレーション・ノース・アメリカ・インコーポレーテッド | Boroaluminosilicate molecular sieve and method of using it for isomerization of xylene |
| CN105883849B (en) * | 2016-07-04 | 2017-11-10 | 山西大同大学 | The synthetic method of the molecular sieves of ZSM 5 of morphology controllable |
| 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 |
| CN114426287B (en) * | 2020-09-28 | 2023-06-06 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and synthesis 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 CN201110214507.3A patent/CN102897791B/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 |
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