CN1119282C - Silicon molecular sieve and its preparing process - Google Patents
Silicon molecular sieve and its preparing process Download PDFInfo
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- CN1119282C CN1119282C CN 00123577 CN00123577A CN1119282C CN 1119282 C CN1119282 C CN 1119282C CN 00123577 CN00123577 CN 00123577 CN 00123577 A CN00123577 A CN 00123577A CN 1119282 C CN1119282 C CN 1119282C
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- molecular sieves
- molecular sieve
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Abstract
The present invention relates to a silicon molecular sieve in an MF 1 crystal structure and a method for the preparation thereof. The crystal grain surfaces of the molecular sieve are cavity concave and convex surfaces. The BET specific surface area is larger than 450 m<2>/g, and the outer specific surface area is larger than 50m<2>/g. The desorption branch and the adsorption branch of low-temperature nitrogen adsorption of the present invention have hysteresis loops between P/P0-[0]=0.45 to 0.98. The silicon molecular sieve is obtained by using organic alkali liquid for processing the silicon molecular sieve prepared by the prior art. When the molecular sieve is used for preparing caprolactam by the gas-phase Beckmann rearrangement reaction of cyclohexanone oxime, and compared with the similar molecular sieve in the prior art, the molecular sieve is helpful for oxime conversion and caprolactam generation.
Description
Technical field
The invention relates to a kind of preparation of si molecular sieves, more specifically say so about the preparation method of si molecular sieves with MFI crystalline structure.
Technical background
Si molecular sieves can be made the material of membrane sepn, also can make the catalyzer that Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement is produced hexanolactam.The coesite that discloses in USP2876072 is the earliest by the crystal silicon oxide of the molecular sieve type of synthetic, and it is to use steam, and strong acid or organic huge legendary turtle are closed reagent the crystalline aluminosilicate of molecular sieve type is handled, and extracts that aluminium in the tetrahedron skeleton forms.
The si molecular sieves that discloses in USP4061724 has the crystalline structure of MFI, does not have the aluminium source in its preparation raw material, has only silicon source, alkali source, template and water, is different from the si molecular sieves that extracts framework aluminum and form, and is direct synthetic si molecular sieves.The used silicon of this si molecular sieves source is a kind of in silicon sol, silicon gel or the white carbon black, and it is to consist of 150～700H by mole
2O: 13～50SiO
2: 0～6.5M
2O: Q
2The reaction mixture of O is 50～150 hours synthetic of hydrothermal crystallizing under 100～250 ℃, autogenous pressure, and wherein, M is a basic metal, and Q is that molecular formula is R
4X
+The season positively charged ion, R represents hydrogen or the alkyl of 2～6 carbon atoms is arranged, X is phosphorus or nitrogen.
Disclosed MFI structure si molecular sieves among the JP59164617 is to be the silicon source with tetraethoxy (TEOS), and TPAOH is the template preparation.At CATAL.REV.-SCI.ENG., 39 (4), studies show that among the 395-424 (1997) is that silicon source synthetic si molecular sieves has total specific surface of very high BET and outer surface area with the tetraethoxy, can reach 400 meters respectively
2/ restrain and 15～30 meters
2/ gram, and the increase of the selectivity of the transformation efficiency of oxime and lactan and outer surface area is proportional.
Summary of the invention
One of purpose of the present invention is on the basis of existing technology, and a kind of si molecular sieves that has improved the MFI crystalline structure of materialization constitutional features is provided.Two of purpose of the present invention provides the preparation method of this si molecular sieves.
MFI crystalline structure si molecular sieves provided by the invention, grain surface is empty male and fomale(M﹠F), the BET specific surface area is greater than 430 meters
2/ gram and outer specific surface are greater than 50 meters
2/ gram, the absorption of its cryogenic nitrogen absorption is propped up with desorption and is propped up at P/P
0There is hysteresis loop between the=0.45-0.98.
Si molecular sieves provided by the present invention, its X-ray diffraction (XRD) spectrogram and " MicroporousMaterials ", Vol 22, p637, the MFI construction standard XRD spectra feature of record is just the same on 1998, has the MFI crystalline structure; From transmission electron microscope photo as can be seen, its grain surface is different from the form that existing si molecular sieves crystal grain shows fully, is empty male and fomale(M﹠F).
Preferred 430～500 meters of the BET specific surface area of si molecular sieves provided by the present invention
2/ gram, preferred 50～100 meters of outer specific surface
2/ gram.
The cryogenic nitrogen adsorption curve of si molecular sieves provided by the present invention is at p/p
0Form hysteresis loop=0.45～0.98 interval the separation, and prop up and there is not hysteresis loop in desorption between propping up substantially with the absorption that the cryogenic nitrogen of the si molecular sieves of prior art for preparing adsorbs.
The preparation method of si molecular sieves provided by the invention is with by weight, after the si molecular sieves that ordinary method synthesizes, organic bases and water mix with 1: 0.05～0.5: 0～8 mixing match, in closed reactor, 100～150 ℃ were reacted 0.1～10 day under the autogenous pressure, reclaimed product then.
The mixing match of the si molecular sieves that said ordinary method synthesizes, organic bases and water is preferred 1: 0.1～0.3: 0.1～2, preferred 0.5～5 day of reaction times.
Also said process can be repeated once or several times among the said preparation method of the present invention.
The ordinary method of said synthetic si molecular sieves among this preparation method, can be method, the method for JP59-164617 record or the method for other bibliographical information that USP4061724 records and narrates, wherein preferably adopting tetraethoxy be that silicon source and TPAOH are the si molecular sieves of alkali source, template preparation.
Described organic bases is selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them, wherein preferred quaternary amine alkali compounds.
The general formula of described fat amine compound is R
1(NH
2)
n, R
1For having the alkyl of 1～6 carbon atom, n=1 or 2, one of the preferred ethamine of fat amine compound, n-Butyl Amine 99, Tri N-Propyl Amine, quadrol or hexanediamine.
The general formula of described alcamine compound is (HOR
2)
mNH
(3-m), R
2For having the alkyl of 1～4 carbon atom, m=1,2 or 3, one of the preferred monoethanolamine of alcamine compound, diethanolamine or trolamine.
Said quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom, wherein preferred tetraethyl ammonium hydroxide or TPAOH.
Therefore si molecular sieves provided by the present invention is applied in the production of hexanolactam because bigger specific surface and the outer specific surface of si molecular sieves that provides than prior art is provided, and can improve the selectivity of the transformation efficiency and the lactan of oxime.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of embodiment 1 sample of doing.
Fig. 2 is the cryogenic nitrogen adsorption-desorption thermoisopleth of embodiment 1 sample of doing.
Fig. 3 is the transmission electron microscope photo of embodiment 1 sample of doing.
Embodiment
Below will the present invention is further illustrated with example.
The BET specific surface of si molecular sieves sample, outer specific surface data and adsorption-desorption thermoisopleth adsorb instrument automatically by U.S.'s Micromeritics ASAP-2400 type and make in the example, the X-ray diffraction spectroscopic data is made by the D5005D type diffractometer of German SIEMENS company, and the grain surface form of sample is by the Hitachi H-800 of NEC company type transmissioning electric mirror determining.
Embodiment 1
The TPAOH aqueous solution 55 grams according to 60 grams of method synthetic si molecular sieves among the embodiment 1 of JP59-164617 and 22.5% mix, 150 ℃ of following crystallization are 1 day in sealed reactor, washing after filtration,, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 475 meters
2/ gram, outer specific surface are 64 meters
2/ gram, the X-ray diffraction spectrogram of product is seen Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption is seen Fig. 2; Transmission electron microscope photo is seen Fig. 3.
Example 2
The TPAOH aqueous solution 55 grams according to former powder 60 grams of the synthetic si molecular sieves of method among the embodiment 1 of JP59-164617 and 22.5% mix, 130 ℃ of crystallization are 3 days in sealed reactor, washing after filtration,, 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 482 meters
2/ gram, outer specific surface are 69 meters
2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 3
The TPAOH aqueous solution 55 grams according to 1 synthetic si molecular sieves 60 grams of embodiment among the USP4061724 and 22.5% mix, 110 ℃ of crystallization are 4 days in sealed reactor, after filtration, washing, and 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 468 meters
2/ gram, outer specific surface are 60 meters
2/ gram.The X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 4
Embodiment 1 synthetic si molecular sieves 60 grams according to JP59-164617 mix with 44 gram quadrols, 150 ℃ of following crystallization are 5 days in sealed reactor, after filtration, washing, and 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 466 meters
2/ gram, outer specific surface are 60 meters
2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 5
Mix according to embodiment 1 synthetic si molecular sieves 60 gram and 72 of the JP59-164617 diamines of restraining oneself, 150 ℃ of following crystallization are 4 days in sealed reactor, after filtration, washing, and 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.The X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 6
Embodiment 1 synthetic si molecular sieves 50 grams of JP59-164617 are mixed with 65 gram monoethanolamines, 130 ℃ of following crystallization are 3 days in sealed reactor, after filtration, washing, and 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 472 meters
2/ gram, outer specific surface are 60 meters
2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 7
Example 8
Present embodiment is on the basis of embodiment 1 preparation process to be repeated once.
Si molecular sieves 60 grams that embodiment 1 is prepared mix with 22.5% the TPAOH aqueous solution 55 grams, 150 ℃ of following crystallization are 1 day in sealed reactor, after filtration, washing, and 110 ℃ of dryings 12 hours, 550 ℃ of roastings 4 hours, si molecular sieves product provided by the present invention.Its BET specific surface area is 485 meters
2/ gram, outer specific surface are 76 meters
2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1; The adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2; Transmission electron microscope photo has the feature of Fig. 3.
Example 9
This example illustrates in vapor phase beckmann rearrangement reaction, the catalyzed reaction result of si molecular sieves provided by the invention.
Reaction unit is a normal pressure continuous flow fixed bed, and reactor inside diameter is 5 millimeters, loadings 0.36 gram of catalyzer, catalyst grain size 20-60 order.
Catalyzer is behind the reaction tubes of packing into, and pre-treatment is 1 hour in normal pressure, 350 ℃ nitrogen atmosphere.
The concentration of cyclohexanone-oxime is 35.7%, and weight space velocity (WHSV) is 7.5, and solvent is a methyl alcohol, and temperature of reaction is 350 ℃, and nitrogen flow is 1.8 liters/hour, 3 hours reaction times.
Reaction product is collected by water cycle cooling back.Capillary gas chromatography, hydrogen flame detector.
Adopting the si molecular sieves of embodiment 1 method preparation among the USP4061724 is catalyzer, and the transformation efficiency of its cyclohexanone-oxime is 69.7%, and the hexanolactam selectivity is 87.5%; And adopt example 1 provided by the invention and 2 si molecular sieves that prepare, and the transformation efficiency of its cyclohexanone-oxime reaches 93.5% and 94.8% respectively, and the selectivity of hexanolactam is respectively 92.3% and 93.2%.More than show si molecular sieves provided by the present invention owing to have unique materialization constitutional features, in the production of hexanolactam, can improve the selectivity of the transformation efficiency and the lactan of oxime.
Claims (10)
1, a kind of preparation method of si molecular sieves of MFI crystalline structure, it is characterized in that will be by weight, the si molecular sieves that synthesizes according to a conventional method: organic bases: the reaction mixture of water=1: 0.05～0.5: 0～8, in closed reactor, 100～150 ℃ were reacted 0.1～10 day under the autogenous pressure, reclaimed product then.
2, according to the described preparation method of claim 1, it is characterized in that will be by weight, the si molecular sieves that synthesizes according to a conventional method: organic bases: the reaction mixture of water=1: 0.1～0.3: 0.1～2, in closed reactor, 100～150 ℃ were reacted 1～5 day under the autogenous pressure, reclaimed product then.
3, according to claim 1 or 2 described preparation methods, it is characterized in that to repeat once or the several times preparation process.
4,, it is characterized in that described organic bases is selected from fat amine compound, alcamine compound, quaternary amine alkali compounds or two or more mixture among them according to claim 1 or 2 described preparation methods.
5, according to the described preparation method of claim 4, the general formula that it is characterized in that described fat amine compound is R
1(NH
2)
n, R
1For having the alkyl of 1～6 carbon atom, n=1 or 2.
6,, it is characterized in that fat amine compound is selected from one of ethamine, n-Butyl Amine 99, Tri N-Propyl Amine, quadrol or hexanediamine according to the described preparation method of claim 5.
7, according to the described preparation method of claim 6, the general formula that it is characterized in that described alcamine compound is (HOR
2)
mNH
(3-m), R
2For having the alkyl of 1～4 carbon atom, m=1,2 or 3.
8,, it is characterized in that described alcamine compound is selected from one of monoethanolamine, diethanolamine or trolamine according to the described preparation method of claim 7.
9,, it is characterized in that described quaternary amine alkali compounds is the alkyl quaternary amine bases compound that contains 1～4 carbon atom according to the described preparation method of claim 4.
10,, it is characterized in that described quaternary amine alkali compounds is tetraethyl ammonium hydroxide or TPAOH according to the described preparation method of claim 9.
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|---|---|---|---|
| CN 00123577 CN1119282C (en) | 2000-08-23 | 2000-08-23 | Silicon molecular sieve and its preparing process |
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|---|---|---|---|
| CN 00123577 CN1119282C (en) | 2000-08-23 | 2000-08-23 | Silicon molecular sieve and its preparing process |
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| CN1119282C true CN1119282C (en) | 2003-08-27 |
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| CN102233277A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Preparation method for catalyst containing MFI structure zeolite |
| CN102432032B (en) * | 2011-09-16 | 2013-05-15 | 湖南大学 | Nanometer all-silicon molecular sieve and its preparation method and use |
| CN103896302B (en) * | 2012-12-28 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of si molecular sieves and preparation method thereof |
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2000
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Granted publication date: 20030827 |