CN112717997B - Preparation method of high-activity catalytic oxidation catalyst TS-1 - Google Patents
Preparation method of high-activity catalytic oxidation catalyst TS-1 Download PDFInfo
- Publication number
- CN112717997B CN112717997B CN202110069156.5A CN202110069156A CN112717997B CN 112717997 B CN112717997 B CN 112717997B CN 202110069156 A CN202110069156 A CN 202110069156A CN 112717997 B CN112717997 B CN 112717997B
- Authority
- CN
- China
- Prior art keywords
- titanium
- silicon
- catalyst
- reaction
- source
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses a preparation method of a high-activity catalytic oxidation catalyst TS-1. The S auxiliary agent is added in the preparation process of the catalyst, the titanium-rich TS-1 molecular sieve catalyst is obtained, meanwhile, the amorphous species on the catalyst is stabilized by the S, the decomposition of hydrogen peroxide can be reduced, and the high-activity catalytic oxidation catalyst is obtained.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a preparation method of a propylene liquid-phase epoxidation catalyst.
Background
The titanium silicalite TS-1 is a molecular sieve catalyst with excellent performance and catalytic oxidation function. Since 1983, the US4410501 patent first reported the synthesis of a TS-1 molecular sieve having the same MFI topology as the ZSM-5 molecular sieve, due to Ti4+Ion substitution of Al in regular molecular sieve framework3+Ions, Ti having hexacoordinating ability on the surface of TS-14+Ions having the potential to accept an electron pair, pair H2O2Has unique adsorption activation performance, can selectively oxidize various organic compounds, and is applied to industrial production in the processes of phenol hydroxylation, cyclohexanone ammoxidation and olefin epoxidation.
The theoretical content extreme value of framework titanium in the titanium silicalite molecular sieve obtained by the traditional preparation method is 2.5 percent, so the quantity of active centers of the titanium silicalite molecular sieve is limited, and the activity of the catalyst is further limited. Therefore, how to obtain the TS-1 molecular sieve rich in framework titanium is a difficulty of a titanium silicalite molecular sieve, and a great deal of work is also done by the researchers. However, the obtained titanium-rich catalyst generates more non-framework titanium and amorphous titanium species, and therefore, the application of the TS-1 molecular sieve catalyst is influenced, so that the post-treatment is mostly needed to eliminate the adverse effects.
Disclosure of Invention
In order to make up the defects of the prior art, the chemical composition of the preparation method of the propylene liquid phase epoxidation catalyst provided by the invention is TS-1.
The invention is realized by the following technical scheme:
a catalyst for preparing propylene oxide by propylene or chloropropene liquid-phase epoxidation reaction and a preparation method thereof are characterized in that: the preparation method of the catalyst specifically comprises the following steps:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a silicon source hydrolysate A;
(2) uniformly mixing a titanium source and a complexing agent, dropwise adding the mixture into the silicon source hydrolysate A, and uniformly stirring to obtain a silicon-titanium hydrolysate B;
(3) heating the silicon-titanium hydrolysate B to remove alcohol, supplementing corresponding water, and adding an S auxiliary agent to obtain silicon-titanium gel C;
(4) and (3) filling the silicon-titanium gel C into a crystallization kettle, crystallizing at the temperature of 150-210 ℃ for 20-120h to obtain a crystallized product, and filtering, separating, drying, washing and roasting to obtain the titanium-silicon molecular sieve TS-1.
Further, the S auxiliary agent in the step (3) is one or a mixture of two of ammonium sulfite and ammonium bisulfite.
Further, the titanium-silicon ratio of the titanium-silicon molecular sieve is 31-33; the content of framework titanium is 3.0-3.2 wt%;
further, the composition of the substance molar ratio in the silicon-titanium gel C in the step (3) is SiO2:TiO2: template agent: and (2) S auxiliary agent: h2O is 1: (0.033-0.05): (0.25-0.4): (0.001-0.01): (25-30); the molar composition of the silicon-titanium gel C is preferably SiO2:TiO2: template agent: and (2) S auxiliary agent: h2O=1:(0.035-0.05):(0.25-0.4):(0.002-0.008):(25-30)。
Further, the drying temperature in the step (4) is preferably 80-120 ℃, and the roasting temperature is preferably 500-650 ℃.
Preferably, in the step (1), the silicon source is one or a mixture of more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate.
Further, the template agent in the step (1) is tetrapropylammonium hydroxide (TPAOH).
Preferably, in the step (2), the titanium source is one or a mixture of more of tetraethyl orthotitanate, tetrabutyl orthotitanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride, and more preferably tetrabutyl orthotitanate.
Further, in the step (2), the complexing agent is one of isopropanol, acetylacetone and ethanol.
The catalyst prepared by the invention can be applied to propylene liquid-phase epoxidation reaction or chloropropene liquid-phase epoxidation reaction.
The liquid phase epoxidation reaction process of the propylene is as follows: adding the catalyst into a reaction kettle, and adding 1.5-5.0mol/L H2O2The reaction temperature of the methanol solution is maintained at 30-50 ℃, the propylene pressure is 2.0-4.0Mpa, and the reaction time is 0.5-3 h; the mass concentration of the titanium silicalite TS-1 in the catalytic system is 0.2-1%.
Specifically, the liquid phase propylene epoxidation reaction is carried out in a batch tank reactor. 0.4g of titanium silicalite TS-1 is added into a stainless steel batch reactor as a catalyst, and 3.5mol/L H is added2O270g of methanol solution, wherein the reaction temperature is maintained at 35 ℃, the propylene pressure is 3Mpa, and the reaction time is 1 h; then cooling, taking the feed liquid to analyze the product composition, and titrating the residual H by adopting a potentiometric titration method2O2The molar concentration of (c).
The chloropropene liquid-phase epoxidation reaction process comprises the following steps: adding the catalyst into a reaction kettle, and adding 3.1-3.4mol/L H2O280g of methanol solution and 60-75g of chloropropene, the reaction temperature is maintained at 35-50 ℃, the reaction pressure is 0.25-0.5Mpa, the reaction time is 1.5-3H, then the temperature is reduced, the feed liquid is taken out to analyze the composition of the product, and the residual H is analyzed by adopting potentiometric titration2O2The molar concentration of (c).
Advantages of the inventionThe effect is as follows: adding an S auxiliary agent in the preparation process of the titanium silicalite TS-1, wherein the S auxiliary agent can greatly reduce the pH value of a synthetic glue solution, so as to slow down the crystallization process, and enable the crystallization process to be matched with the speed of Ti entering a framework and the growth of crystals, thereby obtaining the titanium-rich TS-1 molecular sieve with the framework titanium content of 3.1%; and S in the auxiliary agent can also stabilize amorphous titanium generated in the synthesis process to form Ti-S-O bonds, stabilize the amorphous titanium and prevent H from being decomposed2O2The titanium-silicon molecular sieve has excellent epoxidation activity, and the selectivity of the product and the effective utilization rate of hydrogen peroxide are greatly improved.
Detailed Description
Comparative example 1
Mixing 45g of SiO2Adding 30% silica sol into a jacketed three-neck flask, adding 5.6g of TPABr and 90g of water, and stirring at normal temperature for 0.5h to obtain a silicon source hydrolysate; dissolving 3.8g of tetrabutyl titanate in 6.0g of acetylacetone, stirring for 15min to obtain a titanium source hydrolysate, dropwise adding the titanium source hydrolysate into the silicon source hydrolysate, and stirring for 0.5 h; finally, 18g of n-butylamine is added, stirring is carried out for 1h, the obtained solution is filled into a crystallization kettle, crystallization is carried out for 3d at 175 ℃, and the crystallized product is washed and dried and then washed by 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting at 550 ℃ in air for 6 hours to obtain TS-1-A with the Si/Ti ratio of 51.0 through XRF test.
Comparative example 2
Adding 46.2g of tetraethyl orthosilicate into a beaker, stirring, adding 44g of 25 wt% TPAOH aqueous solution and 38g of water, and hydrolyzing at 30 ℃ for 2 hours to obtain a silicon source hydrolysis mixture; dissolving 3.8g of tetrabutyl titanate in 18.7g of isopropanol, and then stirring for 30min to obtain a titanium source hydrolysis mixture; mixing a hydrolysis mixture of a titanium source and a silicon source, removing alcohol at 80 ℃ for 1.5h, supplementing water for 50.2g, stirring for 30min, filling the obtained transparent glue solution into a crystallization kettle for crystallization, crystallizing at 170 ℃ for 36h, washing and drying the obtained crystallized product, and washing with 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting at 550 ℃ in air for 6 hours to obtain the TS-1-B with the Si/Ti ratio of 51.2 through XRF test.
Example 1
Adding 46.2g of tetraethyl orthosilicate into a beaker, stirring, adding 44g of 25 wt% TPAOH aqueous solution and 38g of water, and hydrolyzing at 30 ℃ for 2 hours to obtain a silicon source hydrolysis mixture; dissolving 3.8g of tetrabutyl titanate in 18.7g of isopropanol, and then stirring for 30min to obtain a titanium source hydrolysis mixture; mixing a hydrolysis mixture of a titanium source and a silicon source, removing alcohol at 80 ℃ for 1.5h, supplementing an aqueous solution containing 0.05g of ammonium sulfite and 50.2g of water, stirring for 30min, putting the obtained transparent glue liquid into a crystallization kettle for crystallization, crystallizing at 170 ℃ for 36h, washing and drying the obtained crystallized product, and washing with a 1M HCl aqueous solution (the liquid-solid ratio is 50ml g)-1) And roasting at 550 ℃ in air for 6 hours to obtain the TS-1-C with the Si/Ti ratio of 32.0 through XRF test.
Example 2
Example 1 was repeated, the amounts of tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate in the preparation of TS-1 were changed to the amounts of tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate in the preparation of TS-1, and after crystallization, washing and drying were carried out, and then washing was carried out with 1M aqueous HCl (liquid-solid ratio: 50ml g/g)-1) And roasting the mixture for 6 hours at 550 ℃ in air, wherein the obtained TS-1 samples with the Si/Ti ratios of 31.9, 31.8 and 32.0 obtained by XRF test have the following code numbers: TS-1-D, TS-1-E, TS-1-F.
Example 3
Example 1 was repeated, tetrabutyl titanate in the preparation of TS-1 was replaced with tetramethyl titanate, tetraethyl titanate and tetrapropyl titanate, the amounts of the component substances were kept constant, and after crystallization, washing and drying were carried out, and then washing with 1M aqueous HCl (liquid-solid ratio: 50ml g/g)-1) And roasting the mixture for 6 hours in air at 550 ℃, and XRF testing the mixture to obtain TS-1 samples with Si/Ti ratios of 31.8, 32.0 and 31.7 respectively, wherein the TS-1 samples are numbered as follows: TS-1-G, TS-1-H, TS-1-I.
Example 4
Example 1 was repeated, the complexing agent in the preparation of TS-1 was replaced with isopropanol and ethanol, the amounts of the component substances were kept constant, and after crystallization, washing and drying were carried out, followed by washing with 1M HCl aqueous solution (liquid-to-solid ratio 50ml g/g)-1) Roasting in air at 550 ℃ for 6 hours, and XRF testing to obtain TS-1 samples with Si/Ti ratios of 31.9 and 32.0 respectively, and numbering:TS-1-J、TS-1-K。
Example 5
Example 1 was repeated, the amount of the S auxiliary agent replaced with the ammonium bisulfite component in the preparation of TS-1 was kept constant, and after crystallization, washing and drying were carried out, and then washing was carried out with 1M HCl aqueous solution (liquid-solid ratio: 50ml g/g)-1) And roasting the mixture for 6 hours in air at 550 ℃, and XRF testing the mixture to obtain TS-1 samples with Si/Ti ratios of 32.1 respectively, wherein the TS-1 samples are numbered as follows: TS-1-L.
Example 6
The liquid phase propylene epoxidation reaction is carried out in a batch kettle reactor. 0.4g of titanium silicalite TS-1 is added into a stainless steel batch reactor as a catalyst, and 3.5mol/L H is added2O270g of methanol solution, keeping the reaction temperature at 35 ℃, controlling the propylene pressure at 3Mpa, charging 40g of propylene, and controlling the reaction time to be 1 h; then cooling, taking the feed liquid to analyze the product composition, titrating the residual H by adopting a potentiometric titration method2O2The molar concentration of (c).
The results are shown in Table 1. Wherein, UH2O2The effective utilization rate of hydrogen peroxide is shown, and the calculation mode is 100% of the amount of the substance generated by PO/the amount of the substance consumed by hydrogen peroxide.
TABLE 1 TS-1 sample Performance data for catalyzing propylene to propylene oxide
Samples | XH2O2/% | SPO/% | UH2O2% |
TS-1-A | 55.8 | 85.1 | 70.5 |
TS-1-B | 70.5 | 90.8 | 80.6 |
TS-1-C | 90.3 | 96.3 | 86.5 |
TS-1-D | 90.6 | 96.1 | 87.5 |
TS-1-E | 90.5 | 96.3 | 87.1 |
TS-1-F | 90.4 | 96.0 | 87.3 |
TS-1-H | 90.6 | 96.9 | 87.1 |
TS-1-I | 90.7 | 96.1 | 87.8 |
TS-1-J | 90.5 | 96.4 | 87.2 |
TS-1-K | 90.5 | 96.2 | 87.0 |
TS-1-L | 90.6 | 96.4 | 87.0 |
As can be seen from the results in Table 1, due to the addition of the S auxiliary agent, the activity of the catalyst is greatly improved, so that the conversion rate and selectivity of hydrogen peroxide and the effective utilization rate of hydrogen peroxide are greatly improved. This effect is not obtained without the addition of auxiliaries.
The chloropropene epoxidation reaction is carried out in a batch kettle reactor. 0.5g of titanium silicalite TS-1 is added into a metal batch reaction kettle as a catalyst, and 3.2mol/L H is added2O280g of methanol solution, and 70g of chloropropene is added; maintaining the reaction temperature at 40 deg.C, the system pressure at 0.3Mpa, and the reaction time at 2H, cooling, collecting the material liquid, analyzing the product composition, and analyzing the residual H by potentiometric titration2O2The molar concentration of (c).
The results are shown in Table 2. Wherein, UH2O2The effective utilization rate of hydrogen peroxide is shown, and the calculation mode is the amount of the generated substances/the consumed substances of hydrogen peroxide is 100%.
TABLE 2 TS-1 sample Performance data for catalyzing epichlorohydrin production
Samples | XH2O2/% | SPO/% | UH2O2% |
TS-1-A | 53.8 | 80.1 | 70.5 |
TS-1-B | 65.5 | 85.8 | 80.6 |
TS-1-C | 91.3 | 96.3 | 87.5 |
TS-1-D | 91.6 | 96.1 | 87.5 |
TS-1-E | 91.5 | 96.3 | 87.1 |
TS-1-F | 91.4 | 96.0 | 87.3 |
TS-1-H | 91.6 | 96.9 | 87.1 |
TS-1-I | 91.7 | 96.1 | 87.8 |
TS-1-J | 91.5 | 96.4 | 87.2 |
TS-1-K | 91.5 | 96.2 | 87.0 |
TS-1-L | 91.6 | 96.4 | 87.0 |
The results in table 2 show that the addition of the S additive improves the activity of the catalyst, greatly improves the conversion rate of hydrogen peroxide, the selectivity of PO and the effective utilization rate of dicationic water, and cannot be realized without the addition of the S additive.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (10)
1. A preparation method of a catalyst TS-1 for liquid-phase epoxidation reaction of propylene or chloropropene is characterized by comprising the following steps:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a silicon source hydrolysate A;
(2) uniformly mixing a titanium source and a complexing agent, dropwise adding the mixture into the silicon source hydrolysate A, and uniformly stirring to obtain a silicon-titanium hydrolysate B;
(3) heating the silicon-titanium hydrolysate B to remove alcohol, supplementing corresponding water and adding an S auxiliary agent to obtain silicon-titanium gel C;
(4) the silicon-titanium gel C is filled into a crystallization kettle and crystallized for 20-120h at the temperature of 150-210 ℃ to obtain a crystallization product, and the titanium-silicon molecular sieve TS-1 is obtained after filtration, separation, drying, washing and roasting;
the S auxiliary agent is one or a mixture of ammonium sulfite and ammonium bisulfite; the complexing agent is one of isopropanol, acetylacetone and ethanol.
2. The production method according to claim 1,
the titanium-silicon ratio of the titanium-silicon molecular sieve is 31-33; the content of framework titanium is 3.0-3.2 wt%;
the silicon-titanium gel C in the step (3) has the composition of SiO in the molar ratio2:TiO2: template agent: and (2) S auxiliary agent: h2O=1:(0.033-0.05):(0.25-0.4):(0.001-0.01):(25-30);
In the step (4), the drying temperature is 80-120 ℃, and the roasting temperature is 500-650 ℃.
3. The method according to claim 2, wherein the molar ratio of the substances in the silicon-titanium gel C in the step (3) is SiO2:TiO2: template agent: and (2) S auxiliary agent: h2O=1:(0.035-0.05):(0.25-0.4):(0.002-0.008):(25-30)。
4. The preparation method according to claim 1, wherein in the step (1), the silicon source is one or a mixture of more of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate; the template agent is tetrapropylammonium hydroxide.
5. The method according to claim 1, wherein in the step (2), the titanium source is one or more of tetraethyl orthotitanate, tetrabutyl orthotitanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride.
6. The production method according to claim 5, wherein the titanium source is tetrabutyl orthotitanate.
7. A catalyst prepared by the method of any one of claims 1 to 6.
8. Use of the catalyst of claim 7 in liquid phase epoxidation of propene or liquid phase epoxidation of chloropropene.
9. The use according to claim 8, wherein in the liquid phase epoxidation of propylene, the catalyst is added into a reaction kettle, and 1.5-5.0mol/L of H is added2O2The reaction temperature of the methanol solution is maintained at 30-50 ℃, the propylene pressure is 2.0-4.0Mpa, and the reaction time is 0.5-3 h; the mass concentration of the catalyst in the catalytic system is 0.2-1%.
10. The use of claim 8, wherein the catalyst is added into a reaction kettle in the liquid phase epoxidation reaction of chloropropene, and 3.1-3.4mol/L of H is added2O2Methanol solution and 60-75g chloropropene, the reaction temperature is maintained at 35-50 ℃, the reaction pressure is 0.25-0.5Mpa, the reaction time is 1.5-3h, and then the temperature is reduced to take feed liquidAnalyzing the product composition, and analyzing the residual H by potentiometric titration2O2The molar concentration of (c).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110069156.5A CN112717997B (en) | 2021-01-19 | 2021-01-19 | Preparation method of high-activity catalytic oxidation catalyst TS-1 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110069156.5A CN112717997B (en) | 2021-01-19 | 2021-01-19 | Preparation method of high-activity catalytic oxidation catalyst TS-1 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112717997A CN112717997A (en) | 2021-04-30 |
CN112717997B true CN112717997B (en) | 2022-02-15 |
Family
ID=75592391
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110069156.5A Active CN112717997B (en) | 2021-01-19 | 2021-01-19 | Preparation method of high-activity catalytic oxidation catalyst TS-1 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112717997B (en) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030091504A1 (en) * | 2001-11-15 | 2003-05-15 | Gary Pasquale | Method for controlling synthesis conditions during molecular sieve synthesis using combinations of quaternary ammonium hydroxides and halides |
CN100457622C (en) * | 2001-12-28 | 2009-02-04 | 大连理工大学 | Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application |
TWI480100B (en) * | 2011-04-27 | 2015-04-11 | China Petrochemical Dev Corp Taipei Taiwan | Titanium-silicon molecular sieve and its preparation method and method for producing cyclohexanone oxime using the molecular sieve |
CN102502688A (en) * | 2011-10-31 | 2012-06-20 | 大连理工大学 | Titanium silicon molecular sieve modifying method based on mixed solution of TPAOH (tetrapropylammonium hydroxide) with sulfur-contained metal salts |
CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
CN111153414A (en) * | 2020-01-16 | 2020-05-15 | 大连理工大学 | Rapid hydrothermal synthesis method of titanium silicalite TS-1 |
-
2021
- 2021-01-19 CN CN202110069156.5A patent/CN112717997B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN112717997A (en) | 2021-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100555100B1 (en) | Crystalline mww-type titanosilicate, its preparation and use thereof for producing epoxides | |
JP4270901B2 (en) | Titanosilicate, method for producing the same, and method for producing an oxidized compound using titanosilicate | |
CN112717998B (en) | High-activity phenol hydroxylation titanium silicalite molecular sieve catalyst and preparation method thereof | |
CN112871205A (en) | Preparation method of high-activity low-byproduct propylene gas-phase epoxidation catalyst | |
CN111036290A (en) | Preparation method of titanium silicalite molecular sieve for inhibiting byproduct generation in propylene epoxidation process | |
CN106082261A (en) | A kind of Ti MWW molecular sieve and preparation method thereof | |
CN111017946B (en) | Preparation method of titanium-containing molecular sieve for olefin epoxidation process | |
CN101307039A (en) | Method for producing epoxide | |
CN112742472B (en) | Preparation method of epoxidation catalyst with high activity and low byproduct | |
US6054112A (en) | Process for the preparation of titanium containing molecular sieves | |
CN112844468A (en) | Catalyst for preparing epoxypropane by propylene gas-phase epoxidation and preparation method thereof | |
CN112717997B (en) | Preparation method of high-activity catalytic oxidation catalyst TS-1 | |
CN107999124B (en) | Core-shell structure Ti-MWW @ Si molecular sieve and preparation and application thereof | |
CN1177758C (en) | Method for the production of a titanium-containing zeolite | |
CN101591024A (en) | A kind of method of modifying of HTS | |
CN109593033B (en) | Method for oxidizing cyclohexanone | |
CN112744836A (en) | Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction | |
CN112871206B (en) | Preparation method of low-cost high-activity phenol hydroxylation titanium silicalite molecular sieve catalyst | |
CN113578377A (en) | Synthetic method of pore-enlarging Ti-MWW molecular sieve | |
JPH10506366A (en) | Process for producing hydroxylamine from ammonia or the corresponding amine, hydrogen and oxygen | |
CN108793182B (en) | Low-cost titanium-silicon molecular sieve, preparation and application thereof | |
CN113443635A (en) | Titanium-containing Beta molecular sieve and synthesis method thereof | |
CN107999125B (en) | Preparation and application of microporous-mesoporous-containing Ti-MWW molecular sieve with core-shell structure | |
CN115650249B (en) | Method for preparing high-performance TS-1 titanium silicalite molecular sieve at low cost | |
CN114225961B (en) | Catalyst for synthesizing epoxypropane and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |