CN102897791A - Synthesis method for ZSM-5 molecular sieve - Google Patents
Synthesis method for ZSM-5 molecular sieve Download PDFInfo
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- CN102897791A CN102897791A CN2011102145073A CN201110214507A CN102897791A CN 102897791 A CN102897791 A CN 102897791A CN 2011102145073 A CN2011102145073 A CN 2011102145073A CN 201110214507 A CN201110214507 A CN 201110214507A CN 102897791 A CN102897791 A CN 102897791A
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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, more specifically say the preparation 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 a kind of low cost, single-autoclave yield rate ZSM-5 molecular sieve preparation method high, simple flow.
The invention provides a kind of preparation method of ZSM-5 molecular sieve, may further comprise the steps:
(1) organic formwork agent is mixed the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source
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, wherein, TPAOH accounts for molar percentage 30～80% in the said organic formwork agent;
(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
Preparation method provided by the invention, reduced and existing contained the sodium technical system and prepare a series of processes such as the needed ammonium exchange of Hydrogen ZSM-5 molecular sieve, filtration, roasting, but with without the raw material of sodium ion as raw materials, 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 preparation were established 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 preparation cost.In addition, the ZSM-5 molecular sieve that the inventive method prepares, its SiO
2/ Al
2O
3Mol ratio 15～280, elementary crystal grain is at 0.05～0.5 μ m, relative crystallinity at least 95%.
Preparation method provided by the invention behind the Crystallization of Zeolite, filters the mother liquor that obtains and can also continue 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 a kind of preparation method of ZSM-5 molecular sieve, may further comprise the steps:
(1) organic formwork agent is mixed the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source
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, wherein, the molar percentage 30～80% of TPAOH in the said organic formwork agent;
(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.
In the method provided by the invention, said organic formwork agent is selected from the mixture of TPAOH and other quaternary ammonium hydroxide or aliphatic amide in the step (1), and wherein TPAOH accounts for the 30-80% molar percentage, and preferred 50～80%.Said other quaternary ammonium hydroxide is selected from Tetramethylammonium hydroxide and/or tetraethyl ammonium hydroxide; It is several that said aliphatic amide is selected from n-Butyl Amine 99, ethamine and the propylamine one or more.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, 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 1～30: 1.
Method provided by the invention, said silicon source can be selected from silica gel and/or white carbon black in the step (2), wherein preferred silica gel.The 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
2Preferred 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 110～150 ℃, more preferably 120～140 ℃ lower processed more preferably 24～36 hours 15～75 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.
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.XRD measures at SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep velocity is 2 °/minute.
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%.
The grain size of molecular sieve adopts scanning electronic microscope to measure.
Embodiment 1～5 explanation molecular sieve preparation method provided by the invention.
Embodiment 1
Take by weighing 2.87 gram aluminium hydroxide (Beijing Chemical Plant, analytical pure, Al
2O
3Content 35%), with 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) mixes mixture mol ratio organic formwork agent/Al
2O
3=5.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 58.98g water mix mixture mol ratio SiO
2/ Al
2O
3=50, H
2O/SiO
2=8.Mixture carried out hydrothermal crystallizing 24 hours in 140 ℃ 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 95% 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 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) mixes mixture mol ratio 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 3 hours, afterwards, with itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO
2Content 98.4%) and 50.65g water mix mixture mol ratio SiO
2/ Al
2O
3=200, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 30 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 97% of molecular sieve S-2, silica alumina ratio 183.The elementary grain size of S-2 is 100～300nm.
Embodiment 3
Take by weighing 0.64 gram aluminum oxide (Chang Ling catalyst plant, Al
2O
3Content 98%), with 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%) mix mixture mol ratio 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 2 hours, afterwards, with itself and 30g silica gel (Qingdao Marine Chemical Co., Ltd., SiO
2Content 98.4%) and 59.69g water mix mixture mol ratio SiO
2/ Al
2O
3=80, H
2O/SiO
2=9.Mixture carried out hydrothermal crystallizing 36 hours in 125 ℃ 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 60～300nm.
Embodiment 4
Take by weighing 0.45 gram pseudo-boehmite (Chang Ling catalyst plant, Al
2O
3Content 75%), with 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) mixes mixture mol ratio 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 3 hours, afterwards, with itself and 30g white carbon black (Shenyang Chemical Co., Ltd., SiO
2Content 99%) and 47.16g water mix mixture mol ratio SiO
2/ Al
2O
3=150, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 24 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-4.
The degree of crystallinity 95% of molecular sieve S-4, silica alumina ratio 133.The elementary grain size of S-4 is 400～500nm.
Embodiment 5
Take by weighing 0.84 gram pseudo-boehmite (Chang Ling catalyst plant, Al
2O
3Content 75%), (the good friend in Beijing contains the new technology development center with itself and the 30.02g TPAOH aqueous solution, analytical pure, TPAOH content 25%) and the 13.58g tetraethyl ammonium hydroxide aqueous solution (Shanghai immortality chemical reagent work, analytical pure, TEAOH content 40%) mix mixture mol ratio organic formwork agent/Al
2O
3=12.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 39.27g water mix mixture mol ratio SiO
2/ Al
2O
3=80, H
2O/SiO
2=7.Mixture carried out hydrothermal crystallizing 30 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-5.
The degree of crystallinity 99% of molecular sieve S-5, silica alumina ratio 75.The elementary grain size of S-5 is 50～150nm.
Claims (7)
1. the preparation method of a ZSM-5 molecular sieve may further comprise the steps:
(1) organic formwork agent is mixed the Al in the mixture in organic formwork agent and the aluminium source with the aluminium source
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, wherein, TPAOH accounts for 30～80 % by mole in the said organic formwork agent;
(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 preparation method of claim 1, wherein, the said organic formwork agent of step (1) is selected from the mixture of TPAOH and other quaternary ammonium hydroxide or aliphatic amide, and wherein TPAOH accounts for 50～80 % by mole.
3. according to the preparation method of claim 2, wherein, said other quaternary ammonium hydroxide is selected from Tetramethylammonium hydroxide and/or tetraethyl ammonium hydroxide; It is several that said aliphatic amide is selected from n-Butyl Amine 99, ethamine and the propylamine one or more.
4. according to the preparation 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.
5. according to the preparation 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.
6. according to the preparation method of claim 1, wherein, the said silicon of step (2) source is silica gel.
7. according to the preparation method of claim 1, wherein, in the said mixture of step (2) in mole, SiO
2/ Al
2O
3Be 40～150, H
2O/SiO
2Be 6～8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102122A (en) * | 2013-03-15 | 2015-11-25 | Bp北美公司 | Boroaluminosilicate molecular sieves and methods for using same for xylene isomerization |
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| 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 |
| 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 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105102122A (en) * | 2013-03-15 | 2015-11-25 | Bp北美公司 | Boroaluminosilicate molecular sieves and methods for using same for xylene isomerization |
| CN105883849A (en) * | 2016-07-04 | 2016-08-24 | 山西大同大学 | Synthesis method of appearance-controllable ZSM-5 molecular sieve |
| 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 |
| 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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|---|---|
| CN102897791B (en) | 2014-12-31 |
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