CN1796278A - Method for preparing silicon-aluminum molecular sieve in EUO structure - Google Patents
Method for preparing silicon-aluminum molecular sieve in EUO structure Download PDFInfo
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- CN1796278A CN1796278A CN 200410102816 CN200410102816A CN1796278A CN 1796278 A CN1796278 A CN 1796278A CN 200410102816 CN200410102816 CN 200410102816 CN 200410102816 A CN200410102816 A CN 200410102816A CN 1796278 A CN1796278 A CN 1796278A
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Abstract
This invention describes a process for preparing an EUO-structured siallitic molecular sieve, comprising the steps of: hydrolyzing aluminum and silicon resources in the aqueous solution of the template agent R; removing the alcohol at 30~100 deg.C; adding the fluoride to obtain the reactant mixture of (0.05~0.7)R:(0.01~0.2)Al2O3:SiO2:(0.4~2)F-1:(2~100)H2O; crystallizing at 120~220 deg.C for 1h to 30d and recovering the product. The said aluminum resource is selected from aluminum isopropanol or aluminum isobutanol, the silicone resource is selected from ethyl silicate, propyl silicate or butyl silicate, and the said template agent R is dihydroxyl hexane diamine. The process uses the fluoride as the mineralizer, and the prepared molecular sieve has outstanding molecular sieve thermal stability, hydrothermal stability and acidity property.
Description
Technical field
The invention relates to a kind of preparation method of Si-Al molecular sieve, further say so about a kind of preparation method of EUO structure Si-Al molecular sieve.
Background technology
Molecular sieve with EUO structure was issued (USP4537754) first by people such as John L.Casci in European patent Eur.Pat.Appl.42226 in 1981, because its unique pore passage structure, reduce the catalytic performance that has excellence in the pour point reactions such as (USP20030127356) at dimethylbenzene isomery (USP 20010051757), content of wax oil product, therefore have good commercial and be worth and application prospect.
The preparation process of this molecular sieve is to prepare a kind of aqueous mixture earlier, and this mixture contains at least a quadrivalent element oxide compound YO
2, at least a trivalent element oxide compound X
2O
3Alkyl derivative with the following polymethylene α-ω diamines of at least a structural formula:
Said alkyl derivative is defined as Q
2+, be a kind of degradation product or precursor of amine, wherein n changes between 3～12, R
1～R
6Can contain 1～8 carbon atom for identical or different hydro carbons or hydroxyl hydro carbons group, 5 R can be arranged at the most
1～R
6Group can be hydroxyl, mixture has the mol ratio of table 1:
Table 1
| Reactant | Available proportioning | Optimum ratio |
| YO 2/X 2O 3： | Be at least 10 | 10～150 |
| OH -/YO 2： | 0.1～6.0 | 0.1～1.0 |
| (M ++Q)/X 2O 3： | 0.5～100 | |
| H 2O/YO 2： | 1～100 |
In the table, X is Si or Ge, and Y is one or more among Al, Fe, Ga, the B, and M is a kind of basic metal or amine, and Q is the alkyl derivative of previous said polymethylene diamines, a kind of degradation product of amine or precursor, perhaps Xiang Guan compound.
Said mixture is crystallization under spontaneous pressure, also can add gas, as nitrogen etc., crystallization temperature is 85～250 ℃, crystallization time can for 1 hour to some months, molecular sieve up to said EUO structure forms, and the length of crystallization time depends on the composition of reaction mixture and the temperature of reaction.
The method that adopts dimethylbenzene dimethyl amine ion to synthesize the molecular sieve of EUO structure as template is disclosed among the Eur.Pat.Appl.159845; G.N.Rao, people such as P.N.Joshi are at document Synthesis andcharacterization of high silica EU-1 (Zeolites, 1989, Vol 9,483) in delivered toluene dimethyl amine and chlorination toluene mixture the method that adopts as the molecular sieve of the synthetic EUO structure of template.
USP6,342, adopt the method that adds crystal seed to synthesize the molecular sieve of EUO structure in 200, selected crystal seed can be the molecular sieve of LTA, LTL, FAU, MOR, MAZ, OFF, FER, ERI, BEA, MFI, MTW, MTT, LEV, TON, NES structure, it also can be the molecular sieve of the EUO structure formed by different chemical with want synthetic molecular sieve, preferred LTA, FAU, MOR, MFI structure molecular screen, and Y '/X ' is lower than 200 EUO structure molecular screen.Reaction mixture has the chemical constitution of table 2 oxide form:
Table 2
| Reactant (mol/mol) | Available proportioning | Optimum ratio | Optimal proportion |
| YO 2/X 2O 3 | At least 10 | At least 12 | At least 25 |
| OH -/YO 2 | 0.002～2 | 0.005～1.5 | 0.01～1 |
| Q/YO 2 | 0.002～2 | 0.005～1.5 | 0.01～1 |
| Q/(M ++Q) | 0.1～1 | 0.1～1.0 | 0.1～1 |
| H 2O/YO 2 | 1～500 | 3～250 | 5～100 |
| P/ | 0～5 | 0～1 | 0～0.25 |
| S/YO 2(g/g) | 0.0001～0.1 | 0.0005～0.07 | 0.001～0.04 |
The same meaning of said Y, X, Q, M and table 1 representative in the table 2, P represents basic metal or amine salt, S represents crystal seed, mixture is crystallization under the pressure that produces automatically, also can add gas, as nitrogen etc., temperature is 85～250 ℃, time can for 1 minute to some months, form up to the molecular sieve of said EUO structure.
The molecular sieve stability of prior art for preparing is poor, when particularly preparing molecular sieve with the inorganic silicon-aluminum source, because the skewness of part aluminium atom makes thermostability and hydrothermal stability on the low side.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of new EUO structure Si-Al molecular sieve, prepared Si-Al molecular sieve constant product quality, and have good thermostability and hydrothermal stability.
Preparation method with molecular sieve of EUO structure provided by the invention, it is characterized in that this method is hydrolysis in the aqueous solution of template R with aluminium source and silicon source, catch up with alcohol at 30～100 ℃, add fluorochemical, obtain mole proportioning and be (0.05～0.7) R: (0.01～0.2) Al
2O
3: SiO
2: (0.4～2) F
-1: (2～100) H
2The reaction mixture of O; Crystallization is 1 hour to 30 days under 120～220 ℃ condition, reclaim product then, wherein said aluminium source is selected from aluminum isopropylate or isobutanol aluminum, said silicon source is selected from tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, said template R is the dihydroxy-hexane diamine, and said fluorochemical is selected from one or more in hydrofluoric acid, alkali-metal fluorochemical and the Neutral ammonium fluoride.。
Among the preparation method provided by the invention, mole proportion optimization (0.2～0.4) R of said reaction mixture: (0.01～0.1) Al
2O
3: SiO
2: (0.4～2) F
-1: (5～50) H
2O.
Among the preparation method provided by the invention, can also in reaction mixture, add crystal seed, said crystal seed can be the molecular sieve of LTA, LTL, FAU, MOR, MAZ, OFF, FER, ERI, BEA, MFI, MTW, MTT, LEV, TON, NES, ITH structure, it also can be the molecular sieve of the EUO structure formed by different chemical with want synthetic molecular sieve, wherein preferred LTA, FAU, MOR, MFI structure molecular screen, the add-on of crystal seed is with SiO in the reaction mixture
2Weight counts 0.5～20%.
Preparation method provided by the invention has overcome the shortcoming of prior art, is mainly reflected in originality and adopts fluorochemical as mineralizer, prepared molecular sieve thermostability and good hydrothermal stability; Has good acidic character.
Description of drawings
Fig. 1 is the XRD spectra of the sample of embodiment 1 preparation.
Fig. 2 is the XRD spectra of the sample of embodiment 6 preparations.
Fig. 3 is among the embodiment 9, the XRD spectra that sample wore out 4 hours down through 800 ℃/100% water vapor conditions.
Embodiment
By the following examples the present invention is further described, but content not thereby limiting the invention.
Among the embodiment, template dihydroxy-hexane diamine is to make by ion-exchange with hexamethonium bromide: the strong-basicity styrene series anion exchange resin splendid attire is in exchange column, and elder generation soaked 2～4 hours with 6% HCl, washed neutrality; Soaked 2～4 hours with about 8% NaOH then, wash neutrality.36.22 hexamethonium bromides (Tokyo changes into) that restrain are dissolved in the water again and form about 10% solution, exchange on the resin of handling well, the solution that exchange is good concentrates under 50 ℃ of conditions with Rotary Evaporators, with the H of 0.1mol/L
2SO
4The solution titration, the dihydroxy-hexane diamine strength of solution of gained is about 0.3993mol/L.
Embodiment 1
The 0.41g aluminum isopropylate is dissolved in the 21.46g tetraethoxy, add then among the dihydroxy-hexane diamine solution 72.62g, mechanical stirring and heating continuously, up to all ethanol and propyl alcohol volatilization, replenish the water of capacity again by proportioning, the last 3.2gHF (40 heavy %) that slowly adds, stirring is a kind of cogelled up to forming, and gel consists of 0.29R: SiO
2: 0.01Al
2O
3: 0.64F
-1: 28H
2O with this gel crystallization 24 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets said crystal.Its XRD crystalline phase figure sees accompanying drawing 1, illustrates that the sample of preparation is the EUO structure.
The 4.08g aluminum isopropylate is dissolved in the positive silicic acid propyl ester of 26.41g, add then among the dihydroxy-hexane diamine solution 50.08g, mechanical stirring and heating continuously, up to all propyl alcohol volatilizations, replenish the water of capacity again by proportioning, the last 2gHF (40 heavy %) that slowly adds, stirring is a kind of cogelled up to forming, and gel consists of 0.2R: SiO
2: 0.1Al
2O
3: 0.4F
-1: 50H
2O, with this gel crystallization 10 days under 170 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, its XRD crystalline phase figure had the feature of accompanying drawing 1.
Embodiment 3
The 2.04g aluminum isopropylate is dissolved in the positive silicic acid propyl ester of 26.41g, add then among the dihydroxy-hexane diamine solution 100.16g, mechanical stirring and heating continuously, up to all propyl alcohol volatilizations, replenish the water of capacity again by proportioning, the last 5gHF (40 heavy %) that slowly adds, stirring is a kind of cogelled up to forming, and gel consists of 0.4R: SiO
2: 0.05Al
2O
3: 1.0F
-1: 50H
2O, with this gel crystallization 2 days under 200 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, gained crystalline XRD crystalline phase figure had the feature of accompanying drawing 1.
Embodiment 4
The 3.84g isobutanol aluminum is dissolved in the 31.35g butyl silicate, adds then among the dihydroxy-hexane diamine solution 100.16g, mechanical stirring and heating continuously, the butanols volatilization up to all replenishes the water of capacity again by proportioning, and the adding quality is SiO
220% MFI structure molecular screen as crystal seed, the last 5.78gNH that slowly adds
4F (96 heavy %), stirring is a kind of cogelled up to forming, and gel consists of 0.1R: SiO
2: 0.08Al
2O
3: 1.5F
-1: 8H
2O, with this gel crystallization 21 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, gained crystalline XRD crystalline phase figure had the feature of accompanying drawing 1.
The 0.48g isobutanol aluminum is dissolved in the 21.46g tetraethoxy, adds then among the dihydroxy-hexane diamine solution 72.62g, mechanical stirring and heating continuously up to all ethanol and butanols volatilization, replenishes the water of capacity again by proportioning, and the adding quality is SiO
210% FAU structure molecular screen as crystal seed, the last 10gHF (40 heavy %) that slowly adds stirs up to forming a kind of cogelledly, gel consists of 0.29R: SiO
2: 0.01Al
2O
3: 2F
-1: 80H
2O, with this gel crystallization 5 days under 180 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, gained crystalline XRD crystalline phase figure had the feature of accompanying drawing 1.
Embodiment 6
The 2.45g aluminum isopropylate is dissolved in the 21.46g tetraethoxy, adds then among the dihydroxy-hexane diamine solution 125.21g, mechanical stirring and heating continuously up to all ethanol and propyl alcohol volatilization, replenishes the water of capacity again by proportioning, and the adding quality is SiO
24% embodiment 1 molecular sieve as crystal seed, the last 5.14gNaF (98 heavy %) that slowly adds stirs up to forming a kind of cogelledly, gel consists of 0.5R: SiO
2: 0.06Al
2O
3: 1.2F
-1: 30H
2O, with this gel crystallization 8 days under 170 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, the gained crystal got XRD crystalline phase figure and sees accompanying drawing 2.
Embodiment 7
Synthesized gel rubber is identical with embodiment 1, and with this gel crystallization 1 day under 210 ℃ of conditions, again with its crystallization 2 days under 140 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, gained crystalline XRD crystalline phase figure had the feature of accompanying drawing 1.
Embodiment 8
The molecular sieve of the foregoing description 1 is distinguished roasting 6 hours under 550 ℃ of conditions, 20 hours and 48 hours, do XRD analysis then, all keep the feature of accompanying drawing 1, its good thermal stability is described.
Embodiment 9
The molecular sieve of the foregoing description 1 was worn out 4 hours and 17 hours respectively under 800 ℃/100% water vapor conditions, do XRD analysis then, its hydrothermal stability is described.
The spectrogram of the sample that 800 ℃/100% water vapor conditions wore out 4 hours is down seen accompanying drawing 3; 800 ℃/100% water vapor conditions aging 17 hours sample down has the feature of spectrogram 3.Senile experiment shows that the molecular sieve of present method preparation has good hydrothermal stability.
Adopt the U.S. 5MX of Nicolet company Fourier transformation infrared spectrometer to measure B acid, the L acid of molecular sieve, the molecular sieve measurement result of embodiment 1 gained is as follows:
Table
| Data embodiment numbering | 200℃ | 350℃ | ||
| Absorbancy/(gram per centimeter 2) | ||||
| L acid | B acid | L acid | B acid | |
| 1 | 7.8 | 5.6 | 7.9 | 5.0 |
| 2 | 13.4 | 11.7 | 13.6 | 11.2 |
| 3 | 9.8 | 7.6 | 9.9 | 7.3 |
| 4 | 10.2 | 8.5 | 10.4 | 8.1 |
| 5 | 8.1 | 5.9 | 8.2 | 5.3 |
| 6 | 9.5 | 7.4 | 9.7 | 6.7 |
| 7 | 7.7 | 5.6 | 7.8 | 4.9 |
Data can illustrate from table, and the molecular sieve of the inventive method preparation has good acidic character.
Claims (4)
1. the preparation method of an EUO structure Si-Al molecular sieve is characterized in that this method is hydrolysis in the aqueous solution of template R with aluminium source and silicon source, catches up with alcohol at 30～100 ℃, adds fluorochemical, obtains mole proportioning and is (0.05～0.7) R: (0.01～0.2) Al
2O
3: SiO
2: (0.4～2) F
-1: (2～100) H
2The reaction mixture of O; Crystallization is 1 hour to 30 days under 120～220 ℃ condition, reclaim product then, wherein said aluminium source is selected from aluminum isopropylate or isobutanol aluminum, said silicon source is selected from tetraethyl orthosilicate, silicic acid orthocarbonate or silicic acid four butyl esters, said template R is the dihydroxy-hexane diamine, and said fluorochemical is selected from one or more in hydrofluoric acid, alkali-metal fluorochemical and the Neutral ammonium fluoride.
2. according to the method for claim 1, the mole proportioning of said reaction mixture is (0.2～0.4) R: (0.01～0.1) Al
2O
3: SiO
2: (0.4～2) F
-1: (5～50) H
2O.
3. according to the method for claim 1, in reaction mixture, add with SiO in the reaction mixture
20.5～20% crystal seed of weight meter, said crystal seed is selected from the molecular sieve of LTA, LTL, FAU, MOR, MAZ, OFF, FER, ERI, BEA, MFI, MTW, MTT, LEV, TON, NES or ITH structure.
4. according to the method for claim 3, said crystal seed is LTA, FAU, MOR or MFI structure molecular screen.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225773A (en) * | 2011-03-18 | 2011-10-26 | 太原理工大学 | Preparation method of molecular sieve |
| CN103429533A (en) * | 2011-01-27 | 2013-12-04 | 日本化学工业株式会社 | Method for producing MTW-type zeolite |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
| CN106283187A (en) * | 2015-05-29 | 2017-01-04 | 武汉理工大学 | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof |
| CN111217376A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Synthesis method of MTW type molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0042226B1 (en) * | 1980-06-12 | 1984-08-08 | Imperial Chemical Industries Plc | Zeolite eu-1 |
| EP0999183B1 (en) * | 1998-11-02 | 2003-06-18 | Institut Francais Du Petrole | Process for the preparation of EUO-type zeolite using structuring agent precursors and use thereof as catalyst for isomerizing eight carbon aromatics |
| DK0999182T3 (en) * | 1998-11-02 | 2003-07-14 | Inst Francais Du Petrole | Process for the preparation of a structure type EUO zeolite by means of the germ of zeolite materials and its use as a catalyst for the isomerization of aromatic compounds with eight carbon atoms |
| ZA997664B (en) * | 1998-12-23 | 2001-06-14 | Inst Francais Du Petrole | Euo zeolite comprising crystals and aggregates of crystals with specific granulometrys and its use as a catalyst in the isomerisation of C8 aromatic compounds. |
| FR2808519B1 (en) * | 2000-05-05 | 2002-08-02 | Inst Francais Du Petrole | LOW SI / AL EUO STRUCTURAL TYPE ZEOLITE AND ITS USE AS A CATALYST FOR ISOMERIZING C8 AROMATIC CUTS |
-
2004
- 2004-12-28 CN CNB2004101028161A patent/CN100363258C/en active Active
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|---|---|---|---|---|
| CN103429533A (en) * | 2011-01-27 | 2013-12-04 | 日本化学工业株式会社 | Method for producing MTW-type zeolite |
| CN103429533B (en) * | 2011-01-27 | 2016-04-13 | UniZeo株式会社 | The manufacture method of MTW type zeolite |
| CN105800644A (en) * | 2011-01-27 | 2016-07-27 | UniZeo株式会社 | Method for producing MTW-type zeolite |
| CN105800644B (en) * | 2011-01-27 | 2018-05-11 | 三井金属矿业株式会社 | The manufacture method of MTW type zeolites |
| CN102225773A (en) * | 2011-03-18 | 2011-10-26 | 太原理工大学 | Preparation method of molecular sieve |
| CN103979574A (en) * | 2014-06-05 | 2014-08-13 | 郑州大学 | Method for synthesizing molecular sieve by using solid phase |
| CN103979574B (en) * | 2014-06-05 | 2016-03-30 | 郑州大学 | The method of solid phase synthesis molecular sieve |
| CN106283187A (en) * | 2015-05-29 | 2017-01-04 | 武汉理工大学 | A kind of ordered big hole-mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline with opal structural and synthetic method thereof |
| CN106283187B (en) * | 2015-05-29 | 2019-04-26 | 武汉理工大学 | A kind of mesoporous multi-stage porous Si-Al molecular sieve ZSM-5 monocrystalline of ordered big hole-with opal structural and its synthetic method |
| CN111217376A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Synthesis method of MTW type molecular sieve |
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