CN1554483A - Composite titanium-silicon catalyst and its preparation and use - Google Patents
Composite titanium-silicon catalyst and its preparation and use Download PDFInfo
- Publication number
- CN1554483A CN1554483A CNA2003101208687A CN200310120868A CN1554483A CN 1554483 A CN1554483 A CN 1554483A CN A2003101208687 A CNA2003101208687 A CN A2003101208687A CN 200310120868 A CN200310120868 A CN 200310120868A CN 1554483 A CN1554483 A CN 1554483A
- Authority
- CN
- China
- Prior art keywords
- composite
- catalyst
- reaction
- cyclohexanone
- silicon
- 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
Landscapes
- Catalysts (AREA)
Abstract
A kind of composite titanium-silicon catalyst capable of used in the ammoxidation of alicyclic ketone, the epoxidation of olefin and hydroxylation of arene is provided. The catalyst is powder comprising titanium-silicon molecular sieve in MFI structure 5.0-90.0 wt% and graphite 10.0-95.0 wt%. The catalyst is prepared via introducing graphite powder into hydrothermal titanium-silicon molecular sieve synthesizing system comprising silicon source, titanium source, template agent, alkali and distilled water. The obtained composite titanium-silicon catalyst may be used in intermittent reactor or slurry bed reactor.
Description
Technical field the present invention relates to a kind of alicyclic ketone ammoxidation, alkene epoxidation, hydroxylated composite Ti-Si catalyst of aromatic hydrocarbons of can be used for.
Background technology U.S. Pat P 4,410,501 had once disclosed HTS (TS-1) of MFI structure and preparation method thereof, it is to be template agent and alkali source with TPAOH (abbreviation TPAOH), is the silicon source with tetraalkyl esters of silicon acis or Ludox, and hydrolyzable titanium compound is the titanium source, they are mixed by certain molar ratio, with mixture in autoclave, under 130 ℃～200 ℃, hydrothermal crystallizing 6～30 days.
The HTS of MFI structure, in a series of catalytic oxidation systems with hydrogen peroxide as oxidant, has superior catalytic performance, it can be applicable in the reactions such as alkene epoxidation, ammoxidation of cyclohexanone, aromatic hydrocarbons hydroxylating, saturated hydrocarbons oxidation, oxidation of alcohols, has the reaction selectivity height, the reaction condition gentleness, characteristics such as technology is simple and safe, and is environmentally friendly.
U.S. Pat P 4,833, and 260 to have introduced with the hydrogen peroxide be oxidant, and the TS-1 molecular sieve is the olefin epoxidation process of catalyst.Reaction temperature is 0～150 ℃, and pressure is 1～100atm., and preferred solvent is methyl alcohol, the tert-butyl alcohol, acetone.With rare hydrogen peroxide is oxidant, and alkene epoxidations such as ethene, propylene, chloropropene, 2-butylene, 1-octene have all obtained result preferably.
J Catal, 1996,161:570 has reported alicyclic ketone and H
2O
2, NH
3Oximation reaction.On the TS-1 molecular sieve catalyst, the active order of alicyclic ketone is: cycloheptanone＞cyclopentanone＞cyclohexanone＞cyclooctanone, cyclohexanone＞2-methyl cyclohexanone=3-methyl cyclohexanone＞2,6-dimethylcyclohexanon.Use is during greater than the TS-1 molecular sieve catalyst of 1.5 μ m, the extending influence significantly of cyclohexanone and oxime thereof; When TS-1 crystal grain during less than 0.3 μ m, oximation reaction is active irrelevant with diffusion, and by the activated centre quantity decision in the TS-1 framework of molecular sieve.
The little crystal grain TS-1 of alicyclic ketone oximation reaction molecular sieve has greater activity, but little crystal grain TS-1 molecular sieve preparation cost height, and separates with the reaction medium difficulty, and carrier disperses, moulding so need to add in commercial Application.German patent DE 4240698 has disclosed activated carbon supported HTS and has been used for the corresponding oxime of alicyclic ketone prepared by ammoxidation, and reaction temperature is 20～120 ℃, NH
3/ ketone=1.2～2.5, hydrogen peroxide/ketone=0.8～1.2, active and selectivity is higher than unsupported HTS.But activated carbon supported HTS can not adopt under the conventional air/oxygen roasting mode to regenerate.
U.S. Pat P 2002/0058840 has introduced HTS and Al
2O
3Adopt the method for extrusion or compressing tablet to carry out moulding, HTS/Al
2O
3=0.1～10: 1, make composite Ti-Si catalyst, be used for the corresponding oxime of alicyclic ketone prepared by ammoxidation of 7～20 carbon atoms.
USP 5,637, and 715 have disclosed in-situ crystallization HTS formation composite Ti-Si catalyst on MFI or MEL structure Si-Al molecular sieve, are used for reactions such as ammoxidation of cyclohexanone.
Do not see so far to have the powdered graphite of inertia is introduced HTS hydro-thermal synthetic system, make composite Ti-Si catalyst, be used for alicyclic ketone ammoxidation, alkene epoxidation, the hydroxylated report of aromatic hydrocarbons.
Summary of the invention the purpose of this invention is to provide a kind ofly to be made up of MFI structure titanium silicon molecular sieve and graphite, is used for the composite Ti-Si catalyst and the preparation thereof of reactions such as alicyclic ketone ammoxidation, alkene epoxidation.
Technical solution of the present invention is, a kind of composite Ti-Si catalyst, the powder of being made up of the graphite of 5.0～90.0% MFI structure titanium silicon molecular sieve and 10.0～95.0% by weight percentage.
The described a kind of composite Ti-Si catalyst of preparation claim 1, adopt the preparation of formed in situ method, be about to powdered graphite and introduce the HTS hydro-thermal synthetic system of forming by silicon source, titanium source, template agent, alkali and distilled water, make HTS growth in situ on powdered graphite, then composite is separated with mother liquor, drying, roasting are made.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in the alicyclic ketone ammoxidation reaction.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in the ammoxidation of cyclohexanone reaction, and ammoxidation of cyclohexanone reaction response temperature is 60～100 ℃, presses the mol ratio, NH
3/ cyclohexanone=1.0～3.0, hydrogen peroxide/cyclohexanone=0.90～1.20, the tert-butyl alcohol, water, acetone or its mixture are solvent, normal pressure.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in alkene epoxidation, and epoxidation reaction temperature is 0～100 ℃, pressure 1～50atm, methyl alcohol, ethanol, acetone or its mixture are solvent, alkene/H
2O
2=1～10: 1.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can be used in epoxidation of propylene and the 1-butylene epoxidation reaction.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst also can be used for reactions such as aromatic hydrocarbons hydroxylating, oxidation of alcohols under common process conditions.
A kind of purposes of composite Ti-Si catalyst, composite Ti-Si catalyst can use in batch still or slurry-bed reaction device.
The synthetic method that adopts U.S. Pat P 4,410,501 to disclose of HTS hydro-thermal is carried out.With TPAOH is template agent and alkali source, is the silicon source with tetraalkyl esters of silicon acis or Ludox, and hydrolyzable titanium compound is the titanium source, they are mixed by certain molar ratio, with mixture in autoclave, under 130 ℃～200 ℃, hydrothermal crystallizing 6～30 days.
The graphite that the present invention introduces in HTS hydro-thermal synthetic system is inertia, and it does not dissolve under strong alkaline condition, can not hinder the HTS crystallization or change the synthetic batching of HTS and form; And Al under the same conditions
2O
3Powder can hinder the HTS crystallization, causes HTS degree of crystallinity to descend; SiO
2Powder is solvable in strong basicity HTS synthetic system, can change the synthetic batching of HTS and form, and causes the decline of gained HTS Ti content, reactivity to reduce.
The graphite that the present invention introduces in HTS hydro-thermal synthetic system is chemically neutral, can not introduce the acid site that promotes side reaction in HTS, the alkali center; Graphite has good heat endurance, can be not destroyed in composite Ti-Si catalyst high-temperature roasting activation or regenerative process.Simultaneously, the graphite carrier that adds in the HTS hydro-thermal is synthetic has played peptizaiton to TS-1 molecular sieve active component, can improve TS-1 molecular sieve utilization rate, reduces TS-1 molecular sieve active component consumption in the reaction.Add and to help that the synthetic back of HTS is separated with mother liquor behind the graphite powder and catalytic reaction finishes separating of rear catalyst and reaction medium.
HTS hydro-thermal synthesis material mixes with powdered graphite, carries out hydro-thermal and synthesize under stirring condition, and is owing to HTS evenly mixes with powdered graphite, better than hydro-thermal synthetic effect under the quiescent conditions.
Effect of the present invention is, the composite Ti-Si catalyst that provides is used for reactivity height such as alicyclic ketone ammoxidation, alkene epoxidation, and selectivity is good, and it is easily separated that reaction finishes the back, Heat stability is good during high-temperature roasting.
The specific embodiment
Comparative Examples 1
This Comparative Examples is to prepare the MFI structure titanium silicon molecular sieve according to the method that embodiment among the USP 4,410,501 1 discloses.
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain product TS-1, and its relative crystallinity is decided to be 100%.
Embodiment 1
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add Al again
2O
3Powder 11.9g was 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/Al of TS-1 50 heavy %
2O
3Product, its relative crystallinity are 36.7%.
Embodiment 2
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add SiO again
2Powder 11.9g was 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/SiO of TS-1 50 heavy %
2Product, its relative crystallinity are 113.6%.
Embodiment 3
Get the 40ml TPAOH and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved in the band teflon-lined autoclave, add powdered graphite 11.9g again, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/ graphite products of TS-1 50 heavy %, and its relative crystallinity is 85.6%.
Comparative Examples 2
The catalytic performance of MFI structure titanium silicon molecular sieve in cyclohexanone ammonia oxygen oxidation reaction that the method that the explanation of this Comparative Examples discloses according to embodiment among the USP 4,410,501 1 prepares.
In 100mL chuck there-necked flask, add 0.3g MFI structure titanium silicon molecular sieve, the 9ml tert-butyl alcohol and 3ml cyclohexanone, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 98.8%; Cyclohexanone oxime selectivity 99.1%.
Embodiment 4
In 100mL chuck there-necked flask, add the TS-1/SiO that contains TS-1 50 heavy % that 0.6g embodiment 2 makes
2Composite Ti-Si catalyst, the 9ml tert-butyl alcohol and 3ml cyclohexanone, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 71.0%; Cyclohexanone oxime selectivity 99.4%.
Embodiment 5
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.6g embodiment 3 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 99.1%; Cyclohexanone oxime selectivity 99.3%.
Embodiment 6
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.45g embodiment 3 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 96.4%; Cyclohexanone oxime selectivity 99.2%.
Embodiment 7
Get the 220ml TPAOH and be dissolved in the 440ml distilled water, under 0～5 ℃, slowly splash in the 253ml silicon tetraethyl acid esters, drip off the back and stir 20min.Splash into 7.48ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 550ml deionized water.Above-mentioned reactant mixture is moved in the 2L high pressure stirred tank, add powdered graphite 65.5g again, 175 ℃ of heating crystallizations 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying in 540 ℃ of roastings 6 hours, obtain containing the TS-1/ graphite products of TS-1 50 heavy %.
Embodiment 8
In 100mL chuck there-necked flask, add the TS-1/ graphite composite Ti-Si catalyst, the 9ml tert-butyl alcohol and the 3ml cyclohexanone that contain TS-1 50 heavy % that 0.45g embodiment 7 makes, gradation adds the ammoniacal liquor of the heavy % in 4.8mL 25 heavy %～28, drips the hydrogen peroxide of 8.0ml 15 heavy % continuously.Magnetic agitation, water bath with thermostatic control temperature control, 80 ℃ of reaction 2h.Reaction is got the laggard circumstances in which people get things ready for a trip analysis of spectrum of supernatant liquor centrifugation after finishing.With sky, the Shanghai U.S. scientific instrument GC7890 of Co., Ltd gas chromatograph analytical reactions product, quartzy capillary chromatograph, fixer are PEG-20M, column length 50m, internal diameter 0.32mm.Reaction result cyclohexanone conversion ratio 99.3%; Cyclohexanone oxime selectivity 99.5%.
Embodiment 9
In the 0.4L stainless steel cauldron, the hydrogen peroxide of the TS-1/ graphite composite Ti-Si catalyst that contains TS-1 50 heavy % that adding 0.6g embodiment 7 makes, 31.6ml methyl alcohol and 2.0ml 30 heavy %.Feed propylene, 0.4MPa keep-ups pressure.Magnetic agitation, water bath with thermostatic control temperature control, 60 ℃ of reaction 1.5h.Reaction finishes back sampling, iodimetric analysis H
2O
2Concentration.With Shanghai analytical instrument factory 1102 type gas chromatograph analytical reactions products, quartzy capillary chromatograph, fixer are PEG-20M, column length 40m.Reaction result hydrogen peroxide conversion ratio 97.4%, expoxy propane selectivity 89.2%.
Embodiment 10
In the 0.4L stainless steel cauldron, the hydrogen peroxide of the TS-1/ graphite composite Ti-Si catalyst that contains TS-1 50 heavy % that adding 0.5g embodiment 7 makes, 31.6ml methyl alcohol and 2.0ml 30 heavy %.Feed the 1-butylene, 0.25MPa keep-ups pressure.Magnetic agitation, water bath with thermostatic control temperature control, 60 ℃ of reaction 1.5h.Reaction finishes back sampling, iodimetric analysis H
2O
2Concentration.With Shanghai analytical instrument factory 1102 type gas chromatograph analytical reactions products, quartzy capillary chromatograph, fixer are PEG-20M, column length 40m.Reaction result hydrogen peroxide conversion ratio 92.1%, epoxy butane selectivity 93.3%.
Claims (6)
1. a composite Ti-Si catalyst is characterized in that, the powder that this catalyst is made up of the graphite of 5.0～90.0% MFI structure titanium silicon molecular sieve and 10.0～95.0% by weight percentage.
2. the method for preparing the described a kind of composite Ti-Si catalyst of claim 1, it is characterized in that, adopt the preparation of formed in situ method, be about to powdered graphite and introduce the HTS hydro-thermal synthetic system of forming by silicon source, titanium source, template agent, alkali and distilled water, make HTS growth in situ on powdered graphite, then composite is separated with mother liquor, drying, roasting are made.
3. the purposes of claim 1,2 described a kind of composite Ti-Si catalysts is characterized in that, composite Ti-Si catalyst can be used in the alicyclic ketone ammoxidation reaction.
4. the purposes of a kind of composite Ti-Si catalyst according to claim 3 is characterized in that, composite Ti-Si catalyst can be used in the ammoxidation of cyclohexanone reaction, and ammoxidation of cyclohexanone reaction response temperature is 60～100 ℃, presses the mol ratio, NH
3/ cyclohexanone=1.0～3.0, hydrogen peroxide/cyclohexanone=0.90～1.20, the tert-butyl alcohol, water, acetone or its mixture are solvent, normal pressure.
5. according to the purposes of claim 1,2 described a kind of composite Ti-Si catalysts, it is characterized in that composite Ti-Si catalyst can be used in alkene epoxidation, epoxidation reaction temperature is 0～100 ℃, pressure 1～50atm, methyl alcohol, ethanol, acetone or its mixture are solvent, alkene/H
2O
2=1～10: 1.
6. the purposes of a kind of composite Ti-Si catalyst according to claim 5 is characterized in that, composite Ti-Si catalyst can be used in epoxidation of propylene and the 1-butylene epoxidation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101208687A CN1296134C (en) | 2003-12-27 | 2003-12-27 | Composite titanium-silicon catalyst and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101208687A CN1296134C (en) | 2003-12-27 | 2003-12-27 | Composite titanium-silicon catalyst and its preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554483A true CN1554483A (en) | 2004-12-15 |
| CN1296134C CN1296134C (en) | 2007-01-24 |
Family
ID=34338330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101208687A Expired - Fee Related CN1296134C (en) | 2003-12-27 | 2003-12-27 | Composite titanium-silicon catalyst and its preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1296134C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311363A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
| CN103012078A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1301999B1 (en) * | 1998-08-05 | 2000-07-20 | Enichem Spa | CATALYST, PROCESS FOR THE PRODUCTION OF OXYGEN WATER AND ITS USE IN OXIDATION PROCESSES. |
| CN1173961C (en) * | 2001-11-14 | 2004-11-03 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
-
2003
- 2003-12-27 CN CNB2003101208687A patent/CN1296134C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311363A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
| CN102311363B (en) * | 2010-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Ammoxidation method for cyclohexanone |
| CN103012078A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
| CN103012078B (en) * | 2011-09-28 | 2015-07-01 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1296134C (en) | 2007-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1110910B1 (en) | A titanium-silicalite molecular sieve and the method for its preparation | |
| CN101291877B (en) | Preparation of titanosilicate zeolite ts-1 | |
| CN1314662C (en) | Process for producing cyclohexanone-oxime | |
| JP2010150274A (en) | Method for producing propylene oxide | |
| US6734323B2 (en) | Process for the preparation of zeolitic catalysts | |
| CN1114495C (en) | Process for preparing composite catalyst and its application | |
| CN1198796C (en) | Process for preparing oxime | |
| CN111924854B (en) | ECNU-29 titanium aluminosilicate nanosheet and preparation method and application thereof | |
| CN110575828A (en) | Efficient catalyst for synthesizing 1, 3-butadiene by reaction of ethanol and acetaldehyde and preparation method thereof | |
| CN106006665B (en) | A kind of preparation method of titanium-silicon molecular sieve TS-1 | |
| CN1173961C (en) | Catalyst for olefine epoxidation | |
| HU214200B (en) | Oxydation catalysts and methods of producing them and their use | |
| CN100425585C (en) | Styrene catalytic oxidation method | |
| CN1119202C (en) | Process for preparing Fe-Si Molecular sieve | |
| CN1111092C (en) | Modifying process for titanium-silicon molecular sieve | |
| CN1296134C (en) | Composite titanium-silicon catalyst and its preparation and use | |
| CN102219234A (en) | Preparation method of nitrogen titanium silicon-containing molecular sieve | |
| CN1140348C (en) | Composite Ti-Si catalyst and its in-situ forming prepn process | |
| CN1076724C (en) | Method for hydroxylation of phenol | |
| CN100417442C (en) | Compound titanium silicon molecular sieve with middle and micro pore, its preparation and use | |
| JP2008200553A (en) | Titanosilicate catalyst | |
| CN108658823B (en) | Process for the preparation of peroxyacetic acid | |
| JP2003327581A (en) | Method for producing propylene oxide | |
| CN110372535B (en) | Modification method of molecular sieve for catalyzing oximation reaction of cyclohexanone | |
| JP3849408B2 (en) | Method for producing pentasil-type crystalline zeolite and method for producing ε-caprolactam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070124 Termination date: 20101227 |