CN1338427A - Silicon molecular sieve and its synthesizing process - Google Patents
Silicon molecular sieve and its synthesizing process Download PDFInfo
- Publication number
- CN1338427A CN1338427A CN 00123576 CN00123576A CN1338427A CN 1338427 A CN1338427 A CN 1338427A CN 00123576 CN00123576 CN 00123576 CN 00123576 A CN00123576 A CN 00123576A CN 1338427 A CN1338427 A CN 1338427A
- Authority
- CN
- China
- Prior art keywords
- gram
- tpaoh
- sio
- molecular sieves
- specific surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A silicon molecular sieve with MFI crystal structure, concave-convex cavities on the surface of its crystal grain, BET specific surface area greater than 430 sq.m/g and external specific surface area greater than 50 sq.m/g is prepared from ethyl silicate as Si source, ammonium tetrapropylhydroxide as alkali source and template agent through crystallizing and treating by organic alkali. It can be used for preparing caprolactam with high transform rate of oxime.
Description
The invention relates to a kind of si molecular sieves and synthetic, more specifically say so about si molecular sieves and synthetic method thereof with MFI crystalline structure.
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 higher BET and outer surface area with the tetraethoxy, can reach 400 meters respectively
2/ restrain and 15～30 meters
2/ gram, and the selectivity of the transformation efficiency of cyclohexanone-oxime and hexanolactam is directly proportional with the increase of outer surface area.
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 synthetic 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, and this shows that this molecular sieve has the MFI crystalline structure; From transmission electron microscope photo as can be seen, be different from existing si molecular sieves grain surface form fully, its grain surface 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, outer specific surface is preferably 50～100 meters
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.
Si molecular sieves provided by the invention can make by following two kinds of methods:
Method one:
(1) tetraethoxy is at room temperature mixed, stirs with TPAOH, fully after the hydrolysis, be warmed up to 70～75 ℃ and kept 3～5 hours, add water, the formation volumetric molar concentration is TPAOH/SiO
2=0.05-0.5, H
2O/SiO
2The mixture of=5-100;
(2) with said mixture in closed reactor, 130～200 ℃ of crystallization are 0.5～10 day under the autogenous pressure, filter then, wash, drying, 400～600 ℃ of roastings 1～10 hour;
(3) be after 1: 0.05～0.5: 0～8 proportioning mixes by weight with product of roasting and organic bases and water, in closed reactor, 100～150 ℃ of reactions 0.1～10 day and reclaim product under the autogenous pressure.
Method two:
(1) tetraethoxy is at room temperature mixed, stirs with TPAOH, fully after the hydrolysis, Jia Shui, add ethanol, the formation volumetric molar concentration is TPAOH/SiO
2=0.05-0.5, EtOH/SiO
2=4-30, H
2O/SiO
2The mixture of=2-100;
(2) with said mixture in closed reactor, 130～200 ℃ of crystallization are 0.5～10 day under the autogenous pressure, filter then, wash, drying, 400～600 ℃ of roastings 1～10 hour;
(3) be after 1: 0.05～0.5: 0～8 proportioning mixes by weight with product of roasting and organic bases and water, in closed reactor, 100～150 ℃ of reactions 0.1～10 day and reclaim product under the autogenous pressure.
Also step (3) can be repeated once or several times in two kinds of synthetic methods provided by the present invention.
The organic bases in the step of said synthetic method (3) and the mixing match of water are preferred 1: 0.1～0.3: 0.1～2, preferred 0.5～5 day of reaction times.
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, positive third ammonium, quadrol or hexanediamine.
The general formula of described alcamine compound is (HOR
2)
mN, 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 (seeing embodiment 9) of the transformation efficiency and the lactan of oxime.
Fig. 1 is the X-ray diffraction spectrogram of embodiment 1 sample.
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.
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.
Example 1
At room temperature 208 gram tetraethoxys (brief note is TEOS) are poured in 1000 ml beakers, stirred 30 minutes, TPAOH with 22.5% (brief note is TPAOH) solution 180 grams add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, stirred 3～5 hours, add water 220 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO
2=0.2, H
2O/SiO
2=20, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 55 gram of getting product of roasting and 22.5% mixes, and 150 ℃ of following crystallization are 1 day in sealed reactor, after filtration, washing, 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 464 meters
2/ gram, outer specific surface are 60 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
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, the 22.5% TPAOH aqueous solution, 180 grams add among the TEOS, stir hydrolysis 2 hours under the room temperature, add water 220 grams, add ethanol (brief note is EtOH) 184 grams, stirring is colloidal sol, and the chemical constitution that mix clear liquid this moment is H
2O/SiO
2=20, EtOH/SiO
2=8, TPAOH/SiO
2=0.20,110 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 55 gram of getting product of roasting and 22.5% mixes, and 150 ℃ of crystallization are 1 day in sealed reactor, after filtration, washing, 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 481 meters
2/ gram, outer specific surface are 70 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
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, add the 22.5% TPAOH aqueous solution, stir hydrolysis 2 hours under the room temperature, add water and ethanol, stir, making the chemical constitution of mixing clear liquid is H
2O/SiO
2=20, EtOH/SiO
2=16, TPAOH/SiO
2=0.20,110 ℃ of crystallization 2 days are filtered, washing, 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
The TPAOH aqueous solution 67.8 gram of getting product of roasting and 22.5% mixes, and 110 ℃ of crystallization are 4 days in sealed reactor, after filtration, washing, 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 488 meters
2/ gram, outer specific surface are 75 meters
2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; 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
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, TPAOH solution 180 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 220 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO
2=0.20, H
2O/SiO
2=20, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 30 gram quadrols mix, 150 ℃ of following crystallization are 5 days in sealed reactor, after filtration, washing, 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 465 meters
2/ gram, outer specific surface are 61 meters
2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; 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
At room temperature 208 gram tetraethoxys are poured in 2000 ml beakers, stirred 30 minutes, TPAOH solution 360 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 440 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO
2=0.40, H
2O/SiO
2=40, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 103 diamines of restraining oneself and mix, 150 ℃ of following crystallization are 4 days in sealed reactor, after filtration, washing, 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 460 meters
2/ gram, outer specific surface are 55 meters
2/ gram, the X-ray diffraction spectrogram of product has the feature of Fig. 1, and the adsorption-desorption spectrogram of cryogenic nitrogen absorption has the feature of Fig. 2, and transmission electron microscope photo has the feature of Fig. 3.
Example 6
At room temperature 208 gram tetraethoxys are poured in 500 ml beakers, stirred 30 minutes, TPAOH solution 90 grams with 22.5% add in the tetraethoxy, stir hydrolysis 2～3 hours under the room temperature, be warmed up to 70～75 ℃, catch up with alcohol to stir 3～5 hours, add water 110 grams, form colloidal sol, stir, volumetric molar concentration is TPAOH/SiO
2=0.1, H
2O/SiO
2=10, said mixture is moved in the stainless steel cauldron of 500 milliliters of inner liner polytetrafluoroethylenes, in 170 ℃ of crystallization 2 days, filter, washing 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting and 76.7 gram monoethanolamines mix, 130 ℃ of following crystallization are 3 days in sealed reactor, after filtration, washing, 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 470 meters
2/ gram, outer specific surface are 59 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
At room temperature 208 gram tetraethoxys are poured in 2000 ml beakers, stirred 30 minutes, the 22.5% TPAOH aqueous solution, 180 grams add among the TEOS, stir hydrolysis 2 hours under the room temperature, add water 220 grams, add ethanol 184 grams, stirring is colloidal sol, and the chemical constitution that mix clear liquid this moment is H
2O/SiO
2=20, EtOH/SiO
2=8, TPAOH/SiO
2=0.20,110 ℃ of crystallization temperatures 2 days filter, washing, 120 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours.
Get product of roasting 30 gram and mix with trolamine 67.5 grams, 120 ℃ of crystallization are 3 days in sealed reactor, after filtration, washing, 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 465 meters
2/ gram, outer specific surface are 62 meters
2/ gram has the feature of Fig. 1 from the X-ray diffraction spectrogram of product; 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 8
Present embodiment be on the basis of example 1 with preparation process in the process of step (3) repeat once.
Molecular sieve 30 grams that example 1 is prepared mix with 22.5% the TPAOH aqueous solution 25 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 497 meters
2/ gram, outer specific surface are 86 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 93.1% and 94.5% respectively, and the selectivity of hexanolactam is respectively 92.1% and 92.9%.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 (13)
1, a kind of si molecular sieves of MFI crystalline structure is characterized in that grain surface is empty male and fomale(M﹠F), and 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.
2,, it is characterized in that the BET specific surface area is 430～500 meters according to the described si molecular sieves of claim 1
2/ gram and outer specific surface are 50～100 meters
2/ gram.
3, the synthetic method of the si molecular sieves of claim 1 is characterized in that building-up process comprises the following steps:
(1) tetraethoxy at room temperature mixed with TPAOH, stir, fully after the hydrolysis, be warmed up to 70～75 ℃ and kept 3～5 hours, add water, the formation volumetric molar concentration is TPAOH/SiO
2=0.05-0.5, H
2O/SiO
2The mixture of=5-100;
(2) with said mixture in closed reactor, 130～200 ℃ of crystallization are 0.5～10 day under the autogenous pressure, filter then, wash, drying, 400～600 ℃ of roastings 1～10 hour;
(3) product of roasting and organic bases and water are mixed with 1: 0.05～0.5: 0～8 weight proportion after, in closed reactor, 100～150 ℃ of reactions 0.1～10 day and reclaim product under the autogenous pressure.
4, the synthetic method of the si molecular sieves of claim 1 is characterized in that building-up process comprises the following steps:
(1) tetraethoxy is at room temperature mixed, stirs with TPAOH, fully after the hydrolysis, Jia Shui, add ethanol, the formation volumetric molar concentration is TPAOH/SiO
2=0.05-0.5, EtOH/SiO
2=4-30, H
2O/SiO
2The mixture of=2-100;
(2) with said mixture in closed reactor, 130～200 ℃ of crystallization are 0.5～10 day under the autogenous pressure, filter then, wash, drying, 400～600 ℃ of roastings 1～10 hour;
(3) product of roasting and organic bases and water are mixed with 1: 0.05～0.5: 0～8 weight proportion after, in closed reactor, 100～150 ℃ of reactions 0.1～10 day and reclaim product under the autogenous pressure.
5,, it is characterized in that to repeat once or several times step (3) according to claim 3 or 4 described synthetic methods.
6, according to claim 3 or 4 described synthetic methods, it is characterized in that step (3) is with product of roasting: organic bases: the weight proportion reaction mixture of water=1: 0.1～0.3: 0.1～2 is in closed reactor, and 100～150 ℃ of reactions are 0.5～5 day and reclaim product under the autogenous pressure.
7,, 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 3 or 4 described synthetic methods.
8, according to the described synthetic method of claim 7, 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.
9,, it is characterized in that fat amine compound is selected from one of ethamine, n-Butyl Amine 99, Tri N-Propyl Amine, quadrol and hexanediamine according to the described synthetic method of claim 8.
10, according to the described synthetic method of claim 7, the general formula that it is characterized in that described alcamine compound is (HOR
2)
mN, R
2For having the alkyl of 1～4 carbon atom, m=1,2 or 3.
11,, it is characterized in that described alcamine compound is selected from one of monoethanolamine, diethanolamine and trolamine according to the described synthetic method of claim 10.
12,, 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 synthetic method of claim 7.
13,, it is characterized in that described quaternary amine alkali compounds is tetraethyl ammonium hydroxide or TPAOH according to the described synthetic method of claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123576 CN1124978C (en) | 2000-08-23 | 2000-08-23 | Silicon molecular sieve and its synthesizing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123576 CN1124978C (en) | 2000-08-23 | 2000-08-23 | Silicon molecular sieve and its synthesizing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1338427A true CN1338427A (en) | 2002-03-06 |
| CN1124978C CN1124978C (en) | 2003-10-22 |
Family
ID=4589973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123576 Expired - Lifetime CN1124978C (en) | 2000-08-23 | 2000-08-23 | Silicon molecular sieve and its synthesizing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1124978C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1386885A1 (en) * | 2002-07-31 | 2004-02-04 | Council of Scientific and Industrial Research | Process for preparing microporous crystalline titanium silicate |
| US7244657B2 (en) | 2002-11-13 | 2007-07-17 | Shin-Etsu Chemical Co. Ltd. | Zeolite sol and method for preparing the same, composition for forming porous film, porous film and method for forming the same, interlevel insulator film, and semiconductor device |
| CN1724366B (en) * | 2004-06-30 | 2010-11-03 | 住友化学株式会社 | Method for manufacturing zeolite and method for manufacturing epsilon-caprolatam |
| 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 |
| CN102050464B (en) * | 2009-10-30 | 2012-07-25 | 中国石油化工股份有限公司 | Synthesizing method of silicon molecular sieve |
| CN103896302A (en) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Silicon molecular sieve and preparation method thereof |
| DE102014222018A1 (en) | 2013-10-29 | 2015-04-30 | China Petroleum & Chemical Corporation | Fully formed of Si molecular sieve and synthesis process for it |
| CN104944440A (en) * | 2014-03-28 | 2015-09-30 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve microporous material and synthesis method thereof |
| CN108318611A (en) * | 2018-01-11 | 2018-07-24 | 华东师范大学 | Based on the capillary open tubular column of silica nanometer zeolite particles and its preparation and application |
| CN112142062A (en) * | 2019-06-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Rare earth-containing silicon molecular sieve with MFI topological structure and preparation method and application thereof |
| CN112138709A (en) * | 2019-06-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Catalyst, preparation method thereof and application of catalyst in cyclohexanone oxime gas-phase Beckmann rearrangement reaction |
-
2000
- 2000-08-23 CN CN 00123576 patent/CN1124978C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1386885A1 (en) * | 2002-07-31 | 2004-02-04 | Council of Scientific and Industrial Research | Process for preparing microporous crystalline titanium silicate |
| US7244657B2 (en) | 2002-11-13 | 2007-07-17 | Shin-Etsu Chemical Co. Ltd. | Zeolite sol and method for preparing the same, composition for forming porous film, porous film and method for forming the same, interlevel insulator film, and semiconductor device |
| US7405459B2 (en) | 2002-11-13 | 2008-07-29 | Shin-Etsu Chemical Co. Ltd. | Semiconductor device comprising porous film |
| CN1724366B (en) * | 2004-06-30 | 2010-11-03 | 住友化学株式会社 | Method for manufacturing zeolite and method for manufacturing epsilon-caprolatam |
| CN102050464B (en) * | 2009-10-30 | 2012-07-25 | 中国石油化工股份有限公司 | Synthesizing method of silicon molecular sieve |
| 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 |
| CN103896302A (en) * | 2012-12-28 | 2014-07-02 | 中国石油化工股份有限公司 | Silicon molecular sieve and preparation method thereof |
| 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 |
| DE102014222018A1 (en) | 2013-10-29 | 2015-04-30 | China Petroleum & Chemical Corporation | Fully formed of Si molecular sieve and synthesis process for it |
| US9656251B2 (en) | 2013-10-29 | 2017-05-23 | China Petroleum & Chemical Corporation | Full-Si molecular sieve and its synthesis process |
| CN104944440A (en) * | 2014-03-28 | 2015-09-30 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve microporous material and synthesis method thereof |
| CN104944440B (en) * | 2014-03-28 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of HTS poromerics and its synthetic method |
| CN108318611A (en) * | 2018-01-11 | 2018-07-24 | 华东师范大学 | Based on the capillary open tubular column of silica nanometer zeolite particles and its preparation and application |
| CN112142062A (en) * | 2019-06-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Rare earth-containing silicon molecular sieve with MFI topological structure and preparation method and application thereof |
| CN112138709A (en) * | 2019-06-28 | 2020-12-29 | 浙江恒澜科技有限公司 | Catalyst, preparation method thereof and application of catalyst in cyclohexanone oxime gas-phase Beckmann rearrangement reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1124978C (en) | 2003-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7785563B2 (en) | Method of the preparation of microporous crystalline molecular sieve possessing mesoporous frameworks | |
| TWI657047B (en) | Full-twist molecular sieve and synthesis method thereof | |
| CN1124978C (en) | Silicon molecular sieve and its synthesizing process | |
| CN101003380B (en) | Method for synthesizing ZSM-5 zeolite with multilevel pore canals | |
| CN109775714B (en) | MFI topological structure silicon molecular sieve containing trace rare earth ions and preparation method thereof | |
| CN112299443B (en) | High-silicon ZSM-5 molecular sieve for adsorbing VOCs (volatile organic compounds), and preparation method and application thereof | |
| CN104556112A (en) | Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof | |
| CN102050464B (en) | Synthesizing method of silicon molecular sieve | |
| CN101003378A (en) | Method for preparing beta zeolite with multilevel pore canals | |
| CN107337215A (en) | A kind of Silicate-1 molecular sieves containing precious metal ion and preparation method thereof | |
| CN104556113A (en) | Method for synthesizing titanium silicate molecular sieve employing organic quaternary ammonium salt template agent | |
| CN108658087B (en) | Hierarchical pore TS-1 zeolite material and preparation method thereof | |
| CN110615445B (en) | Method for synthesizing ZSM-5 zeolite monobloc without template and adhesive | |
| CN1749161A (en) | Hard template synthetic composite hole zeolite molecular sieve and its preparing method | |
| CN1749162A (en) | High molecule polymer template synthetic composite hole zeolite molecular sieve and its preparing method | |
| JPH05254826A (en) | Synthesis of zeolite of mtt type, product obtained and its application in adsorption and catalyst | |
| CN112744831B (en) | Method for preparing titanium-containing molecular sieve, titanium-containing molecular sieve produced by method and cyclohexanone oximation reaction method | |
| CN1119282C (en) | Silicon molecular sieve and its preparing process | |
| CN1040970C (en) | Synthesis of Ti-Si ultra macroporous molecular sieve | |
| CN1327947A (en) | Process for preparing Ti-Si molecular sieve | |
| CN1164576C (en) | Method for synthesizing caprolactam | |
| CN112744834B (en) | Titanium-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method | |
| CN1057066C (en) | Process for synthesizing high-silicon ZSM-5 molecular sieve | |
| CN111099609B (en) | Synthesis method of beta molecular sieve | |
| CN1089279C (en) | Synthesis of titania-silica molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20031022 |