CN102616805A - Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 - Google Patents
Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 Download PDFInfo
- Publication number
- CN102616805A CN102616805A CN2011100303566A CN201110030356A CN102616805A CN 102616805 A CN102616805 A CN 102616805A CN 2011100303566 A CN2011100303566 A CN 2011100303566A CN 201110030356 A CN201110030356 A CN 201110030356A CN 102616805 A CN102616805 A CN 102616805A
- Authority
- CN
- China
- Prior art keywords
- inorganic
- tio
- mol ratio
- source
- molecular sieve
- 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.)
- Pending
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a titanium-silicon-aluminum molecular sieve ETAS-10. The preparation method comprises the following steps of mixing an inorganic silicon source, an inorganic titanium source, an inorganic aluminum source, an inorganic alkali source and water according to a mole ratio of SiO2: TiO2: Al2O3: OH<-1>: H2O of (4.0 to 6.5): 1.0: (0.1 to 0.8): (2.0 to 10.0): (80 to 350) into a synthetic reaction raw material, adding potassium chloride into the synthetic reaction raw material so that in a reaction system, a mole ratio of Cl<-1>: TiO2 is 1.0 to 5.0, stirring uniformly, adjusting a pH value of the reaction system to a pH value of 10.4 to 10.6, carrying out hydro-thermal treatment at a temperature of 180 to 260 DEG C for 24 to 240 hours, and collecting, washing and drying solids. The preparation method provided by the invention has the advantages that cheap inorganic raw materials can be directly synthesized into the titanium-silicon-aluminum molecular sieve ETAS-10 having high purity and high cleanliness easily and conveniently.
Description
Technical field
The present invention is the preparation method of the molecular sieve of silicon-aluminum containing, specifically, is a kind of preparation method of micropore titanium silicon aluminum molecular screen.
Background technology
ETAS-10 is a kind of titanium Si-Al molecular sieve with unique microvoid structure, is the verivate of titanium silicon molecular sieve ETS-4-10, and is open first by USP5244650.Research shows that the ETAS-10 molecular sieve has similar structure with the disclosed ETS-10 molecular sieve of USP4853202.The molecular formula of ETS-10 molecular sieve is (NaK)
2Si
5TiO
13, the skeleton of ETAS-10 molecular sieve is then by the Siliciumatom of tetrahedral coordination, the titanium atom of octahedral coordination and the aluminium atomic building of tetrahedral coordination, [the TiO that such structure forms
6]
2-Make ETS-10 molecular sieve and ETAS-10 skeleton be negativity, and Na
+And K
+Ionic equilibrium is electrical.According to lewis' theory of acids and bases, [TiO
6]
2-Because of there being lone-pair electron to have alkaline nature, in Ti-(OH)-Si structure bridge-type-OH then has acid properties.Compare with other molecular sieve through calculate finding, the acidity of ETS-10 molecular sieve very a little less than.And in the ETAS-10 molecular sieve,, form more highly acid Al-(OH)-Si structure, but to [TiO because Al mainly gets in the silicon-oxy tetrahedron
6]
2-Octahedral structure is influence not.Therefore compare with the ETS-10 molecular sieve, though main skeleton structure of ETAS-10 molecular sieve and ETS-10 molecular sieve are approaching, have the alkalescence close with the ETS-10 molecular sieve, the acidity of TEAS-10 molecular sieve is better than the ETS-10 molecular sieve.The duct of ETAS-10 molecular sieve (being about 0.9nm) is more bigger than the duct (being about 0.7nm) of ETS-10 molecular sieve in addition, and these characteristics make the ETAS-10 molecular sieve will have more wide application in fractionation by adsorption and catalytic field.
At present, in ETAS-10 molecular sieve synthetic, need adding ETS-10 crystal seed, and the synthesis step more complicated of ETS-10 molecular sieve.The synthetic organic formwork agents such as quaternary ammonium salt, aliphatic amide that need of early stage ETS-10 molecular sieve, after serve research work and reported under the condition of organic-free template, also can synthesize and obtain ETS-10, but need a large amount of fluorions, in order to obtain the ETS-10 molecular sieve of high purity and high-crystallinity; Except adding fluorion, also need add a certain amount of crystal seed, like USP4853202, USP4938939, Chem.Commun., 1996; 10,1105, Micropor.Mesopor.Mater., 2002,56; 227, Micropor.Mesopor.Mater., 2005,80,263, Nature; 1994,367,347, Micropor.Mesopor.Mater.; 2005,79,13, USP5453263 all has report.CN200510027074.5 discloses under the condition that does not add fluorion, organic formwork agent and crystal seed and has used Ti
2(SO
4)
3, TiCl
3And TiO
2Method for the synthetic ETS-10 molecular sieve in titanium source.But in ETAS-10 molecular sieve synthetic; Even do not add organic formwork agent, often also need add a certain amount of fluorion and ETS-10 as crystal seed, like the disclosed mode of USP5244650; And in order to obtain the ETAS-10 molecular sieve of high purity and high-crystallinity; A1 introducing amount is limited, have only when Al/Ti than less than 0.35 the time, just can obtain ETAS-10 molecular sieve (the Colloids and Surfaces A:Physicochemical and Engineering Aspects 179 of higher degree and percent crystallinity; 2001,133-138).
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of titanium Si-Al molecular sieve ETAS-10, this method be synthetic microporous titanium sial ETAS-10 molecular sieve under the condition of not using any organic raw material, organic formwork agent, fluorion and crystal seed, has simplified preparation process.
The preparation method of titanium Si-Al molecular sieve ETAS-10 provided by the invention comprises inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 4.0～6.5: 1.0: 0.1～0.8: 2.0～10.0: 80～350 mol ratio is processed the building-up reactions raw material, adds Repone K then, makes Cl in the reaction system
-/ TiO
2Mol ratio is 1.0～5.0, stirs, and the pH value of reaction system is adjusted into 10.4～10.6, and 180～260 ℃ of hydrothermal treatment consists 24～240 hours are collected solid and washing, drying.
The raw material of the synthetic ETAS-10 that the inventive method adopts is inorganic raw material cheap and easy to get; Synthetic system is an alkaline aqueous solution; Obtain product through sol-gel process through hydrothermal treatment consists; Method is simple, easy handling, directly the micropore titanium silicon aluminum molecular screen ETAS-10 of synthesis of high purity and percent crystallinity.Do not use organic formwork agent, fluorion and crystal seed in the building-up process, synthetic system is simplified, and has reduced synthetic cost.
Description of drawings
Fig. 1 is the different al that has of the inventive method preparation
2O
3/ TiO
2The XRD spectra of the ETAS-10 molecular sieve of mol ratio.
Fig. 2 is for the ETAS-10 molecular sieve of the inventive method preparation
27Al solid-state nuclear magnetic resonance spectrogram.
Fig. 3 is for the ETAS-10 molecular sieve of the inventive method preparation
29Si solid-state nuclear magnetic resonance spectrogram.
Fig. 4 is the XRD spectra of the ETAS-10 molecular sieve of the inventive method preparation.
Embodiment
The inventive method is raw material with the inorganics, synthetic microporous titanium sial ETAS-10 molecular sieve under the condition of not using organic formwork agent, fluorion and crystal seed.
The inventive method needs in reaction system, to add Cl after being made into reaction mixture with inorganic raw material and water
-In reaction system, add Cl
-Can use Repone K separately, also can add the mixture of Repone K and sodium-chlor.If add the mixture of Repone K and sodium-chlor, then dosage makes Cl in the reaction system
-/ TiO
2Mol ratio is 1.0～5.0, K
+/ TiO
2Mol ratio is 1.0～10.0, stirs, and the pH value of reaction system is adjusted into 10.4～10.6, carries out hydrothermal crystallizing then, collects solid and also washs, is drying to obtain the ETAS-10 molecular sieve.
The preferred silicon-dioxide in inorganic silicon source described in the inventive method, alkali-metal silicate or silicon sol, described alkali-metal silicate can be water glass or potassium silicate, and the aqueous solution of water glass is commonly called as water glass, and molecular formula is Na
2OmSiO
2, wherein the m value is generally 2.4～3.7, SiO
2Content is 24～30 quality %, Na
2O content is 7～13 quality %.The preferred titanium oxide of described inorganic ti sources, the price that can avoid the existence of titanous chloride and titanium tetrachloride is than costliness and the shortcoming that is easy to hydrolysis.The preferred sodium metaaluminate in described inorganic aluminium source, aluminum chloride or white lake, more preferably sodium metaaluminate, described white lake comprises boehmite and pseudo-boehmite.OH in the reaction system
-1Can provide by inorganic silicon source and inorganic aluminate compound, also can add mineral alkali, like sodium hydroxide or Pottasium Hydroxide.
In the inventive method, the amount in inorganic silicon source is with SiO
2Meter, the amount of inorganic ti sources is with TiO
2Meter, the amount in inorganic aluminium source is with Al
2O
3Meter, the amount of inorganic alkali source is to be present in the OH in the reaction system
-1Meter.When synthesizing the ETAS-10 molecular sieve, preferably inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water are pressed SiO with the inventive method
2: TiO
2: Al
2O
3: OH
-1: H
2O is 4.5～6.0: 1.0: 0.1～0.6: 4.0～8.5: 100～260 mol ratio is processed the building-up reactions raw material, uses Repone K that Cl is provided separately
-The time, preferably make Cl
-/ TiO
2Mol ratio is 1.5～3.0; Use Repone K and sodium-chlor that Cl is provided simultaneously
-The time, preferably make Cl
-/ TiO
2Mol ratio is 1.5～3.0, K
+/ TiO
2Mol ratio is 1.0～7.0.
The inventive method is more preferably pressed SiO with inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water
2: TiO
2: Al
2O
3: OH
-1: H
2O is 5.0～5.5: 1.0: 0.1～0.6: 4.0～8.5: 120～200 mol ratio is processed the building-up reactions raw material, uses Repone K that Cl is provided separately
-The time, more preferably make Cl
-/ TiO
2Mol ratio is 1.5～3.0; Use Repone K and sodium-chlor that Cl is provided simultaneously
-The time, more preferably make Cl
-/ TiO
2Mol ratio is 1.5～3.0, K
+/ TiO
2Mol ratio is 1.0～7.0.
The inventive method is adding Cl in the building-up reactions material system
-After, adopt hydrochloric acid soln to adjust the pH value of synthetic system, make the pH value reach 10.4～10.6.Carry out crystallization with hydrothermal method then, preferred 200～240 ℃, more preferably 220～240 ℃ of hydrothermal temperatures, preferred 72～168 hours of hydro-thermal time, more preferably 96～120 hours.After the hydrothermal treatment consists resultant is filtered, the solids that obtains is through washing the pH value 7～8 to washings, and is dry then, preferred 90～120 ℃ of drying temperature.
The micropore titanium silicon aluminum molecular screen ETAS-10 of the inventive method preparation is widely used in fractionation by adsorption and catalytic field, as is used for the hydrogen cracking of heavy oil and the hydroisomerization of normal paraffin.
Further specify the present invention through instance below, but the present invention is not limited to this.
Instance 1
With sodium silicate solution (service water glass, wherein SiO
2Content is 29 quality %, Na
2O content is 12.8 quality %) be the silicon source, titanium dioxide powder is the titanium source, sodium metaaluminate is the aluminium source, gets 31.3g sodium silicate solution, 2.2g titanium dioxide powder and 0.9g sodium metaaluminate respectively, presses SiO
2: TiO
2: Al
2O
3: OH
-: H
2The O mol ratio is 5.5: 1.0: 0.2: 5.0: 180 the amount mixing (OH that feeds intake
-With contained Na in water glass and the sodium metaaluminate
+Corresponding OH
-Metering), add 3.0g Repone K and 1.7g sodium-chlor then, Cl in the reaction system
-/ TiO
2Mol ratio is 2.5, K
+/ TiO
2Mol ratio is 1.5, stirs to obtain white pulpous state liquid in 0.5 hour, with the HCl solution of 37 quality % system pH is transferred to 10.5, continues to stir 0.5 hour.The colloidal solution that obtains moved into have in the autoclave of teflon lined, 230 ℃ of hydrothermal crystallizings 120 hours.Naturally cool to 30 ℃, products therefrom is filtered, it is 8,120 ℃ of dryings 12 hours that solid uses the pH value of deionized water wash to washings, obtains the white solid powder, forms and sees table 1, and the specific surface area that BET measures is 243m
2/ g, pore volume are 0.175cm
3/ g, its XRD spectra see curve a among Fig. 1, can know that by curve a this pressed powder has the characteristic peak of ETAS-10 molecular sieve, and not have other stray crystal peak, and crystalline phase purity is higher.
Instance 2
With sodium silicate solution (service water glass, wherein SiO
2Content is 29 quality %, Na
2O content is 12.8 quality %) be the silicon source, titanium dioxide powder is the titanium source, sodium metaaluminate is the aluminium source, takes by weighing 31.3g sodium silicate solution, 2.2g titanium dioxide powder and 1.8g sodium metaaluminate respectively, presses SiO
2: TiO
2: Al
2O
3: OH
-: H
2The O mol ratio is 5.5: 1.0: 0.4: 5.4: 180 the amount mixing (OH that feeds intake
-With contained Na in water glass and the sodium metaaluminate
+Corresponding OH
-Metering), add 3.0g Repone K and 1.7g sodium-chlor then, Cl in the reaction system
-/ TiO
2Mol ratio is 2.5, K
+/ TiO
2Mol ratio is 1.5, stirs to obtain white pulpous state liquid in 0.5 hour, with the HCl solution of 37 quality % system pH is transferred to 10.5, continues to stir 0.5 hour.The colloidal solution that obtains moved into have in the autoclave of teflon lined, 230 ℃ of hydrothermal crystallizings 120 hours.Naturally cool to 30 ℃, products therefrom is filtered, it is 8,120 ℃ of dryings 12 hours that solid uses the pH value of deionized water wash to washings, obtains the white solid powder, forms and sees table 1.The specific surface area that BET measures is 230m
2/ g, pore volume are 0.175cm
3/ g, its XRD spectra see curve b among Fig. 1.This pressed powder of curve b explanation has the characteristic peak of ETAS-10 molecular sieve, and does not have other stray crystal peak, and crystalline phase purity is higher.
27Al solid-state nuclear magnetic resonance spectrogram is seen Fig. 2, explains that Al gets in the silicon-oxy tetrahedron, forms acid stronger Al-(OH)-Si structure,
29Si solid-state nuclear magnetic resonance spectrogram is seen Fig. 3, explains that Si is present in the silicon-oxy tetrahedron.
Instance 3
With sodium silicate solution (service water glass, wherein SiO
2Content is 29 quality %, Na
2O content is 12.8 quality %) be the silicon source, titanium dioxide powder is the titanium source, sodium metaaluminate is the aluminium source, takes by weighing 31.3g sodium silicate solution, 2.2g titanium dioxide powder and 3.6g sodium metaaluminate respectively, presses SiO
2: TiO
2: Al
2O
3: OH
-: H
2The O mol ratio is 5.5: 1.0: 0.8: 6.2: 180 the amount mixing (OH that feeds intake
-With contained Na in water glass and the sodium metaaluminate
+Corresponding OH
-Metering), add 3.0g Repone K and 1.7g sodium-chlor then, Cl in the reaction system
-/ TiO
2Mol ratio is 2.5, K
+/ TiO
2Mol ratio is 1.5, stirs to obtain white pulpous state liquid in 0.5 hour, with the HCl solution of 37 quality % system pH is transferred to 10.5, continues to stir 0.5 hour.The colloidal solution that obtains moved into have in the autoclave of teflon lined, 230 ℃ of hydrothermal crystallizings 144 hours.Naturally cool to 30 ℃, products therefrom is filtered, it is 8,120 ℃ of dryings 12 hours that solid uses the pH value of deionized water wash to washings, obtains the pressed powder of white, forms and sees table 1.Its XRD spectra is seen curve c among Fig. 1, and this pressed powder of curve c explanation has the characteristic peak of ETAS-10 molecular sieve, and does not have other stray crystal peak, and crystalline phase purity is higher, and the specific surface area that BET measures is 210m
2/ g, pore volume are 0.170cm
3/ g.
Instance 4
Method by instance 1 prepares the ETAS-10 molecular sieve, different is with reaction raw materials in autoclave in 200 ℃ of hydrothermal crystallizings 120 hours, filter again, wash, drying, the specific surface area of the ETAS-10 molecular sieve that makes is 232m
2/ g, pore volume are 0.174cm
3/ g, its XRD spectra see curve a among Fig. 4, explain that it has the characteristic peak of ETAS-10 molecular sieve, and do not have other stray crystal peak, and crystalline phase purity is higher.
With the silicon dioxide powder is the silicon source, and titanium dioxide powder is the titanium source, and sodium metaaluminate is the aluminium source, and Pottasium Hydroxide provides OH
-, take by weighing 31.3g silicon dioxide powder, 2.2g titanium dioxide powder, 1.8g sodium metaaluminate and 6.9g Pottasium Hydroxide respectively, press SiO
2: TiO
2: Al
2O
3: OH
-: H
2The O mol ratio is 5.5: 1.0: 0.2: the mixing that feeds intake of 4.5: 180 amount adds 3.0g Repone K, Cl in the reaction system then
-/ TiO
2Mol ratio is 1.5, K
+/ TiO
2Mol ratio is 6.0, stirs to obtain white pulpous state liquid in 0.5 hour, with the HCl solution of 37 quality % system pH is transferred to 10.5, continues to stir 0.5 hour.The colloidal solution that obtains moved into have in the autoclave of teflon lined, 230 ℃ of hydrothermal crystallizings 120 hours.Naturally cool to 30 ℃, products therefrom is filtered, it is 8,120 ℃ of dryings 12 hours that solid uses the pH value of deionized water wash to washings, obtains the ETAS-10 molecular sieve solid powder of white, and the specific surface area that BET measures is 240m
2/ g, pore volume are 0.175cm
3/ g, XRD spectra see curve b among Fig. 4, explain that it has the characteristic peak of ETAS-10 molecular sieve, and do not have other stray crystal peak, and crystalline phase purity is higher.
Instance 6
Method by instance 5 prepares the ETAS-10 molecular sieve, and different is that AlCl is used in the aluminium source
3, add Repone K, Cl in the conditioned reaction system
-/ TiO
2Mol ratio is 2.7, K
+/ TiO
2Mol ratio is 6.0, and the specific surface area of the ETAS-10 molecular sieve that after hydrothermal crystallizing, filtration, washing, drying, makes is 235m
2/ g, pore volume are 0.175cm
3/ g, XRD spectra see curve c among Fig. 4, explain that it has the characteristic peak of ETAS-10 molecular sieve, and do not have other stray crystal peak, and crystalline phase purity is higher.
Instance 7
Method by instance 1 prepares the ETAS-10 molecular sieve, different the is aluminium source uses pseudo-boehmite (the SB powder that German Sasol company produces, wherein Al
2O
3Content is 75 quality %).230 ℃ of hydrothermal crystallizings 168 hours, the specific surface area of the ETAS-10 molecular sieve that after filtration, washing, drying, makes was 230m with reaction raw materials
2/ g, pore volume are 0.174cm
3/ g, XRD spectra see curve d among Fig. 4, explain that it has the characteristic peak of ETAS-10 molecular sieve, and do not have other stray crystal peak, and crystalline phase purity is higher.
Table 1
Claims (10)
1. the preparation method of a titanium Si-Al molecular sieve ETAS-10 comprises inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 4.0～6.5: 1.0: 0.1～0.8: 2.0～10.0: 80～350 mol ratio is processed the building-up reactions raw material, adds Repone K then, makes Cl in the reaction system
-/ TiO
2Mol ratio is 1.0～5.0, stirs, and the pH value of reaction system is adjusted into 10.4～10.6, and 180～260 ℃ of hydrothermal treatment consists 24～240 hours are collected solid and washing, drying.
2. according to the described method of claim 1, it is characterized in that in the building-up reactions raw material, adding the mixture of Repone K and sodium-chlor, make Cl in the reaction system
-/ TiO
2Mol ratio is 1.0～5.0, K
+/ TiO
2Mol ratio is 1.0～10.0, stirs, and the pH value of reaction system is adjusted into 10.4～10.6, and 180～260 ℃ of hydrothermal treatment consists 24～240 hours are collected solid and washing, drying.
3. according to claim 1 or 2 described methods, it is characterized in that described inorganic silicon source is silicon-dioxide, alkali-metal silicate or silicon sol.
4. according to claim 1 or 2 described methods, it is characterized in that described inorganic ti sources is a titanium oxide.
5. according to claim 1 or 2 described methods, it is characterized in that described inorganic aluminium source is sodium metaaluminate, aluminum chloride or white lake.
6. according to the described method of claim 1, it is characterized in that inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 4.5～6.0: 1.0: 0.1～0.6: 4.0～8.5: 100～260 mol ratio is processed the building-up reactions raw material, and makes Cl
-/ TiO
2Mol ratio is 1.5～3.0.
7. according to the described method of claim 2, it is characterized in that inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 4.5～6.0: 1.0: 0.1～0.6: 4.0～8.5: 100～260 mol ratio is processed the building-up reactions raw material, and makes Cl
-/ TiO
2Mol ratio is 1.5～3.0, K
+/ TiO
2Mol ratio is 1.0～7.0.
8. according to the described method of claim 1, it is characterized in that inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 5.0～5.5: 1.0: 0.1～0.6: 4.0～8.5: 120～200 mol ratio is processed the building-up reactions raw material, and makes Cl
-/ TiO
2Mol ratio is 1.5～3.0.
9. according to the described method of claim 1, it is characterized in that inorganic silicon source, inorganic ti sources, inorganic aluminium source, inorganic alkali source and water by SiO
2: TiO
2: Al
2O
3: OH
-1: H
2O is 5.0～5.5: 1.0: 0.1～0.6: 4.0～8.5: 120～200 mol ratio is processed the building-up reactions raw material, and makes Cl
-/ TiO
2Mol ratio is 1.5～3.0, K
+/ TiO
2Mol ratio is 1.0～7.0.
10. according to claim 1 or 2 described methods, it is characterized in that drying temperature is 90～120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100303566A CN102616805A (en) | 2011-01-28 | 2011-01-28 | Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100303566A CN102616805A (en) | 2011-01-28 | 2011-01-28 | Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102616805A true CN102616805A (en) | 2012-08-01 |
Family
ID=46557091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100303566A Pending CN102616805A (en) | 2011-01-28 | 2011-01-28 | Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102616805A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556104A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent |
| CN106362682A (en) * | 2016-10-26 | 2017-02-01 | 南京大学 | Biomass gas adsorbent based on dynamic separation and preparation method thereof |
| CN107551991A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of preparation method of heavy metals sorbing material |
| CN108658727A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Propylene method for oxidation |
| CN108658728A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Application of the titanium Si-Al molecular sieve in preparing propylene glycol |
| CN109384656A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN109593072A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | A kind of method of olefin oxidation |
| CN112439451A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof |
-
2011
- 2011-01-28 CN CN2011100303566A patent/CN102616805A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| L. LV ET AL.: "Incorporation of hybrid elements into microporous titanosilicate ETS-10:An approach to improving its adsorption properties toward Pb2+", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556104A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent |
| CN106362682A (en) * | 2016-10-26 | 2017-02-01 | 南京大学 | Biomass gas adsorbent based on dynamic separation and preparation method thereof |
| CN106362682B (en) * | 2016-10-26 | 2018-10-09 | 南京大学 | A kind of biomass gas adsorbent and preparation method thereof based on dynamics separation |
| CN108658727B (en) * | 2017-03-30 | 2022-06-28 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN108658727A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Propylene method for oxidation |
| CN108658728A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | Application of the titanium Si-Al molecular sieve in preparing propylene glycol |
| CN109384656A (en) * | 2017-08-09 | 2019-02-26 | 中国石油化工股份有限公司 | The method for preparing cyclohexanone |
| CN109384656B (en) * | 2017-08-09 | 2021-12-17 | 中国石油化工股份有限公司 | Process for preparing cyclohexanone |
| CN107551991A (en) * | 2017-08-31 | 2018-01-09 | 长沙埃比林环保科技有限公司 | A kind of preparation method of heavy metals sorbing material |
| CN109593072A (en) * | 2017-09-30 | 2019-04-09 | 中国石油化工股份有限公司 | A kind of method of olefin oxidation |
| CN109593072B (en) * | 2017-09-30 | 2020-09-22 | 中国石油化工股份有限公司 | Method for oxidizing olefin |
| CN112439451A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof |
| CN112439451B (en) * | 2019-09-02 | 2022-10-14 | 中国石油化工股份有限公司 | Low-temperature sulfur-tolerant shift catalyst, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102616805A (en) | Preparation method of titanium-silicon-aluminum molecular sieve ETAS-10 | |
| CN102190312A (en) | Method for recycling molecular sieve mother solution | |
| CN102224104B (en) | Molecular sieve ssz-83 | |
| WO2018227849A1 (en) | Molecular sieve scm-14, synthesis method therefor and use thereof | |
| CN106536411A (en) | Synthesis of a boron-containing zeolite with an MWW framework structure | |
| US20120059181A1 (en) | Hybrid, organic-inorganic, crystalline, porous silicates and metal-silicates | |
| CN105555711B (en) | The method for preparing zeolite SSZ 35 | |
| CN108217682A (en) | The method of method synthesis Silicon-rich ZSM-48 zeolite molecular sieves is oriented to using crystal seed | |
| CN101898767B (en) | Synthetic method of high silica ZSM-5 zeolite | |
| WO2016078035A1 (en) | Active aluminosilicate material and preparation method therefor | |
| CN108190913A (en) | The method of method synthesis Silicon-rich ZSM-5 zeolite molecular sieve is oriented to using crystal seed | |
| CN107519933B (en) | Y/EU-1/SBA-15/ASA/MOF composite material and preparation method | |
| JP5693724B2 (en) | Hydrothermal synthesis of zeolites or zeolite-like materials using modified mixed hydroxides | |
| Zubowa et al. | Crystallization of phase-pure zeolite NaP from MCM-22-type gel compositions under microwave radiation | |
| CN1321062C (en) | Process for synthesizing microporous titanium silicon fluorite ETS-10 | |
| CN101125662B (en) | Method for preparing beta zeolite from kaolin | |
| CN101774604A (en) | Method for synthesizing zeolite through acidactivation of attapulgite clay | |
| JPH0648725A (en) | Production of beta-type zeolite | |
| CN109205636A (en) | The preparation method of Y/SAPO-34/ZSM-11/ASA multilevel hole material | |
| JP2526253B2 (en) | Method for producing zeolite Nu-3 | |
| JPS5978922A (en) | Crystalline zeolite and manufacture | |
| CN102341350B (en) | Isomorphous substitution silicate | |
| KR20090049713A (en) | Preparation method of zeolites with high silica/alumina ratio | |
| RU2174952C1 (en) | Method of preparing zeolite | |
| RU2476378C1 (en) | METHOD OF OBTAINING NaY ZEOLITE |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120801 |