CN106582807B - Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction - Google Patents
Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction Download PDFInfo
- Publication number
- CN106582807B CN106582807B CN201510660354.3A CN201510660354A CN106582807B CN 106582807 B CN106582807 B CN 106582807B CN 201510660354 A CN201510660354 A CN 201510660354A CN 106582807 B CN106582807 B CN 106582807B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium
- sieve
- barium
- barium salt
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
A kind of application the invention discloses modifying titanium-silicon molecular sieve and method of modifying and in propylene ring oxidation reaction, barium salt is dissolved in after water is prepared into barium salt aqueous solution, strip Titanium Sieve Molecular Sieve is added, the weight ratio of barium salt, water and strip Titanium Sieve Molecular Sieve is 0.001~0.5:0.1~5:1；1~72h, filtering are impregnated, solid roasts the Titanium Sieve Molecular Sieve being modified to obtain the final product after 4~12h after drying 3~5h at 80~120 DEG C at 500~550 DEG C；Strip Titanium Sieve Molecular Sieve be Titanium Sieve Molecular Sieve original powder and field mountain valley with clumps of trees and bamboo powder, silica solution after mixing extruded moulding and obtain；Barium salt is barium nitrate, barium acetate or barium chloride.Modified molecular sieve is the strip Titanium Sieve Molecular Sieve with MFI structure；Modified molecular sieve is used for liquid propylene epoxidation process as catalyst.Method of modifying of the present invention, operating process is simple, due to the mutual synergistic effect of barium salt and Titanium Sieve Molecular Sieve, the decomposition for making it be applied in propylene ring oxidation reaction that hydrogen peroxide can be significantly reduced effectively improves the effective use of hydrogen peroxide and the selectivity of product propene oxide.
Description
Technical field
The present invention relates to a kind of modifying titanium-silicon molecular sieve and its method of modifying, and further to modified molecular sieve
Application in liquid propylene epoxidation reaction, belongs to technical field of inorganic.
Background technique
Titanium is successfully introduced into pure silica zeolites by nineteen eighty-three Taramasso et al., has synthesized Titanium Sieve Molecular Sieve for the first time
TS-1.Titanium-silicon molecular sieve TS-1 belongs to rhombic system, has MFI topological structure identical with ZSM-5 molecular sieve.Due to transition gold
Belong to the introducing of titanium so that TS-1 is provided with unique catalytic oxidation performance.TS-1 is widely used in alkene epoxidation, alkane
In the catalytic oxidations such as the hydroxylating of partial oxidation, oxidation of alcohols, the oximate of ketone, phenol and benzene.
Hydrogen peroxide is generally acknowledged Green Oxidant, and oxidized byproduct only has water.Late 1970s are it is found that TS-
1 can be used as the catalyst of propylene ring oxidation reaction, and TS-1 has been opened using hydrogen peroxide as oxidizer catalytic alkene epoxidation since then
Prelude.TS-1/H2O2System reaction condition is mild, atom utilization is high, process safety, low in the pollution of the environment, simple process, is
A kind of green chemistry chemical technology new process with broad prospect of application.
If the titanium-silicon molecular sieve TS-1 being synthesized using classical approach is directly used in propylene without subsequent processing
In epoxidization reaction process, then there can be the disadvantages of active low and selectivity of product is poor, simultaneously because leading the characteristics of TS-1 itself
Cause it that there is certain decomposability to hydrogen peroxide itself, this undoubtedly reduces the effective rate of utilization of hydrogen peroxide in reaction, and dioxygen
The O that water decomposition generates2It can be present in reaction system, increase the risk of Chemical Manufacture.Therefore people, which constantly change, is used for
The synthesis of the TS-1 of propylene ring oxidation reaction and method of modifying, to improve the reactivity and product propene oxide of catalyst
Selectivity.
Currently, generally use organic base (such as fatty amines, alcamines, quaternary ammonium alkaloid compound, tetrapropylammonium hydroxide,
Tetraethyl ammonium hydroxide, n-propylamine, hexamethylene diamine), organic amine (diethylamine, triethylamine, tetramethylammonium hydroxide, tetrabutyl hydrogen-oxygen
Change the aqueous solutions such as ammonium), inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid), nitrate or the acetate (nitre of copper, lead, cobalt, nickel, silver etc.
The aqueous solution of hydrochlorate or acetate), soluble magnesium salt (such as magnesium sulfate, magnesium chloride), aluminum soluble salt (such as aluminium chloride, aluminum sulfate, nitre
Sour aluminium), noble metal (Ru, R, Pd, Re, Os, Ir, Pt, Au etc.), organic sequestering agent aqueous slkali (such as 1,2-diaminocyclohexane tetraacetic acid, hydroxyl
Ethyl-3-acetic acid ethylenediamine, ethylenediamine tetra-acetic acid, citric acid, glutamic acid, tartaric acid etc.) etc. place is modified to Titanium Sieve Molecular Sieve
Reason.But above-mentioned modifying agent is all made of crystallizing kettle and carries out at 100~240 DEG C, have certain want to equipment when being modified
It asks, needs to bear certain pressure, treatment process is cumbersome and processing cost is higher；When being modified processing using precious metal salt,
Due to having used precious metal raw material, processing cost is higher；Processing is modified using inorganic acid, it is also desirable to which equipment has
Certain rotproofness, and the waste water discharged is also required to neutralisation treatment.And above-mentioned method of modifying is to molecular screen primary powder
It is modified, modified separation of solid and liquid is extremely difficult (especially to the separation of nanoscale molecular sieve).
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the deficiencies in the prior art, and provide a kind of titanium silicon molecule
The method of modifying of sieve is separated by solid-liquid separation without special consersion unit using strip Titanium Sieve Molecular Sieve after molding as modified object
It is easy to operate；Using the aqueous solution of barium salt as modifying agent, modifying agent is cheap and easy to get, and occurs between barium salt and Titanium Sieve Molecular Sieve
Mutually synergistic effect, so that the Titanium Sieve Molecular Sieve of preparation be made to significantly reduce invalid point to hydrogen peroxide in propylene ring oxidation reaction
Solution, improves the effective rate of utilization of hydrogen peroxide and the selectivity of product propene oxide.
It is a kind of by the modified Titanium Sieve Molecular Sieve of above-mentioned method of modifying the second object of the present invention is to provide.
The third object of the present invention is to provide a kind of above-mentioned modified Titanium Sieve Molecular Sieve during epoxidation of propylene
Using.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of method of modifying of Titanium Sieve Molecular Sieve, comprising the following steps: barium salt is dissolved in the aqueous solution that water is prepared into barium salt
Afterwards, strip Titanium Sieve Molecular Sieve is added, impregnates 1~72h under quiescent conditions and solid is placed in baking oven after filtering removes solution
3~5h is dried under the conditions of 80~120 DEG C, is then placed in again in Muffle furnace after roasting 4~12h under the conditions of 500~550 DEG C, i.e.,
Obtain the modified Titanium Sieve Molecular Sieve of barium monoxide.
In above-mentioned technical proposal, the strip Titanium Sieve Molecular Sieve is Titanium Sieve Molecular Sieve original powder and the field of traditional handicraft preparation
After mixing, silica solution further extruded moulding after mixing, specific steps are as follows: take 20 grams of Titanium Sieve Molecular Sieve are added in mountain valley with clumps of trees and bamboo powder
Original powder after mixing, is added the silica solution of 14 milliliters of 30wt% further after mixing, uses banded extruder with 1 gram of field mountain valley with clumps of trees and bamboo powder
Extruded moulding, it is finally that molding sample is 12 hours dry under the conditions of 100 DEG C, then roasted 6 hours under the conditions of 550 DEG C,
Obtain the strip Titanium Sieve Molecular Sieve with MFI structure.
In above-mentioned technical proposal, the weight ratio of the barium salt, water and strip Titanium Sieve Molecular Sieve is 0.001~0.5:0.1
~5:1.
Preferably, the weight ratio of the barium salt, water and strip Titanium Sieve Molecular Sieve is 0.001~0.1:0.1~2:1.
In above-mentioned technical proposal, the barium salt is appointing in soluble barium salt, such as barium nitrate, barium acetate, barium chloride
It anticipates one kind.
Preferably, the barium salt is barium nitrate or barium acetate.
In above-mentioned technical proposal, the dip time is preferably 12~48h.
In above-mentioned technical proposal, the dipping, drying, roasting and etc. can be repeated one or more times to strip titanium silicon
Molecular sieve is modified.
The present invention also provides a kind of Titanium Sieve Molecular Sieve modified by above-mentioned method of modifying, which is to tie with MFI
The strip Titanium Sieve Molecular Sieve of structure.
The present invention also provides a kind of Titanium Sieve Molecular Sieve modified by above-mentioned method of modifying in liquid propylene epoxidation process
In application, the epoxidation of propylene process is using methanol as solvent, specific reaction condition are as follows: 2.5~3.0Mpa of reaction pressure,
35~40 DEG C of reaction temperature, 0.8~1.2h of propylene air speed-1, propylene and H2O2Molar ratio is 2:1~4:1.
The advantages of technical solution of the present invention, is that modified object is strip Titanium Sieve Molecular Sieve after molding, is separated by solid-liquid separation
It operates very simple；Molecular sieve is modified using barium salt as modifying agent, since barium salt is cooperateed with the mutual of Titanium Sieve Molecular Sieve
Effect, so that modified molecular sieve can significantly reduce the decomposition of hydrogen peroxide in propylene ring oxidation reaction, effectively mentions
The effective use of high hydrogen peroxide and product propene oxide selectivity.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold:
Various reagents used in the embodiment of the present invention are commercially available chemical reagent.
Titanium Sieve Molecular Sieve original powder described in the embodiment of the present invention and comparative example is traditionally
What method described in " Zeolites, page 1992, Vol.12 the 943rd~950 " was prepared, specifically: with ethyl orthosilicate
For silicon source, butyl titanate is titanium source, and tetrapropylammonium hydroxide is template, 150~200 DEG C crystallization 12~48 hours, warp
Be filtered, washed, dry, roast after obtain Titanium Sieve Molecular Sieve original powder.
Comparative example: strip Titanium Sieve Molecular Sieve is prepared
20g Titanium Sieve Molecular Sieve original powder and 1 gram of field mountain valley with clumps of trees and bamboo powder that traditionally prepared by method are taken, is added after mixing
The silica solution of 14 milliliters of 30wt% is further uniformly mixed, and banded extruder extruded moulding is then used, finally by molding sample in 100
It is 12 hours dry under the conditions of DEG C, it is then roasted 6 hours under the conditions of 550 DEG C, obtains strip Titanium Sieve Molecular Sieve, be labeled as TS-1.
Embodiment 1: strip Titanium Sieve Molecular Sieve is modified
After 0.34g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby impregnates for 24 hours under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
A, after measured, the mass fraction of BaO is 0.22% in TS-1-A.
Embodiment 2:
After 0.34g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby, impregnates 48h under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
B, after measured, the mass fraction of BaO is 0.24% in TS-1-B.
Embodiment 3:
After 0.68g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby, impregnates 36h under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
C, after measured, the mass fraction of BaO is 0.49% in TS-1-C.
Embodiment 4:
After 1.36g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby impregnates for 24 hours under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
D, after measured, the mass fraction of BaO is 0.95% in TS-1-D.
Embodiment 5:
After 2.72g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby, impregnates 48h under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
E, after measured, the mass fraction of BaO is 2.1% in TS-1-E.
Embodiment 6:
After 6.8g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements preparation
Made of TS-1, impregnate under quiescent conditions for 24 hours, after filtering removal solution, solid be placed in baking oven and is dried under the conditions of 100 DEG C
Then 4h is placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, be labeled as TS-1-F,
After measured, the mass fraction of BaO is 4.9% in TS-1-F.
Embodiment 7:
After 9.52g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby, impregnates 36h under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
G, after measured, the mass fraction of BaO is 6.1% in TS-1-G.
Embodiment 8:
After 13.6g barium nitrate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby impregnates for 24 hours under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
H, after measured, the mass fraction of BaO is 8.3% in TS-1-H.
Embodiment 9:
After 1.33g barium acetate is dissolved in the aqueous solution for being prepared into barium salt in 30g deionized water, 30g comparison is added and implements system
TS-1 made of standby, impregnates 48h under quiescent conditions, after filtering removal solution, solid is placed in baking oven and is dried under the conditions of 100 DEG C
Dry 4h, is then placed in Muffle furnace after roasting 6h under the conditions of 550 DEG C again, obtains modified Titanium Sieve Molecular Sieve, is labeled as TS-1-
I, after measured, the mass fraction of BaO is 0.97% in TS-1-C.
Application examples:
The Titanium Sieve Molecular Sieve of the embodiment of the present invention and comparative example preparation, it is solid applied to epoxidation of propylene as catalyst
In fixed bed reaction process, catalyst sample is placed in stainless steel jacketed reaction pipe, the inertia porcelain of the both ends φ 3mm of reaction tube
Ball is filled.In reaction process, it is 3.0Mpa that nitrogen, which maintains system pressure, and keeping reaction temperature with thermostatic water-circulator bath is 38
DEG C, reactant hydrogen peroxide and propylene and solvent methanol are fed simultaneously, propylene air speed 0.8h-1, propylene and H2O2Molar ratio is 3；
Product analysis, indicator reaction H are periodically carried out in reaction process2O2Conversion ratio (XH2O2) and effective rate of utilization (UH2O2), Yi Jihuan
Ethylene Oxide selectivity (SPO)。
Strip Titanium Sieve Molecular Sieve and change with 1~9 pair of strip Titanium Sieve Molecular Sieve of the embodiment of the present invention prepared by comparative example
The results are shown in Table 1 in propylene ring oxidation reaction for the molecular sieve obtained after property:
Table 1: result of the different Titanium Sieve Molecular Sieve in propylene ring oxidation reaction
| Catalyst number | XH2O2(%) | SPO(%) | UH2O2(%) |
| TS-1 | 98.2 | 88.2 | 80.1 |
| TS-1-A | 97.7 | 92.5 | 83.7 |
| TS-1-B | 98.1 | 92.3 | 84.0 |
| TS-1-C | 97.9 | 94.6 | 88.2 |
| TS-1-D | 98.1 | 97.8 | 95.5 |
| TS-1-E | 97.6 | 97.0 | 94.7 |
| TS-1-F | 97.2 | 97.6 | 94.2 |
| TS-1-G | 97.8 | 98.2 | 94.4 |
| TS-1-H | 95.8 | 98.4 | 93.8 |
| TS-1-I | 98.4 | 97.9 | 95.3 |
As can be seen from the above table, processing is modified to Titanium Sieve Molecular Sieve using barium salt, propylene epoxy can be significantly improved
Change H in reaction process2O2Effective rate of utilization, and product propene oxide selectivity is also with increasing, but when modified titanium silicon point
Barium monoxide content is improved to after 1% or more in son sieve, H2O2Effective rate of utilization no longer improve.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (9)
1. a kind of method of modifying of Titanium Sieve Molecular Sieve, comprising the following steps: barium salt is dissolved in after water is prepared into the aqueous solution of barium salt,
Strip Titanium Sieve Molecular Sieve is added, impregnates 1~72h under quiescent conditions, after filtering removal solution, solid is placed in baking oven 80~
3~5h is dried under the conditions of 120 DEG C, is then placed in again in Muffle furnace under the conditions of 500~550 DEG C after roasting 4~12h to get oxygen
Change the modified Titanium Sieve Molecular Sieve of barium；
The barium salt is soluble barium salt, and soluble barium salt is barium nitrate, any one in barium chloride.
2. the method according to claim 1, wherein the strip Titanium Sieve Molecular Sieve is by following methods system
Made of standby: the Titanium Sieve Molecular Sieve original powder and 1 gram of field mountain valley with clumps of trees and bamboo powder for taking 20 grams of traditional handicrafts to prepare after mixing, are added 14 milliliters
The silica solution of 30wt% further after mixing, with banded extruder extruded moulding, finally by molding sample under the conditions of 100 DEG C
It is 12 hours dry, the strip Titanium Sieve Molecular Sieve is obtained after then roasting 6 hours under the conditions of 550 DEG C.
3. the method according to claim 1, wherein the weight of the barium salt, water and strip Titanium Sieve Molecular Sieve
Than for 0.001~0.5:0.1~5:1；The water is deionized water.
4. according to the method described in claim 3, it is characterized in that, the weight of the barium salt, water and strip Titanium Sieve Molecular Sieve
Than for 0.001~0.1:0.1~2:1.
5. the method according to claim 1, wherein the soluble barium salt is barium nitrate.
6. the method according to claim 1, wherein the dip time is 12~48h.
7. the method according to claim 1, wherein the dipping, drying, calcination steps can be repeated once
Or repeatedly strip Titanium Sieve Molecular Sieve is modified.
8. a kind of pass through the modified Titanium Sieve Molecular Sieve of the described in any item methods of claim 1~7, which is characterized in that described
Molecular sieve be the strip Titanium Sieve Molecular Sieve with MFI structure.
9. a kind of application of Titanium Sieve Molecular Sieve according to any one of claims 8 as catalyst in liquid propylene epoxidation process,
It is characterized in that, the epoxidation of propylene process is using methanol as solvent, reaction condition are as follows: 2.5~3.0Mpa of reaction pressure, reaction
35~40 DEG C of temperature, 0.8~1.2h of propylene air speed-1, propylene and H2O2Molar ratio is 2:1~4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660354.3A CN106582807B (en) | 2015-10-14 | 2015-10-14 | Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660354.3A CN106582807B (en) | 2015-10-14 | 2015-10-14 | Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582807A CN106582807A (en) | 2017-04-26 |
| CN106582807B true CN106582807B (en) | 2019-02-22 |
Family
ID=58552801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510660354.3A Active CN106582807B (en) | 2015-10-14 | 2015-10-14 | Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582807B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854933B (en) * | 2016-06-21 | 2018-08-14 | 中触媒新材料股份有限公司 | A kind of modifying titanium-silicon molecular sieve and its method of modifying and application |
| CN109999903B (en) * | 2019-04-26 | 2022-08-12 | 中触媒新材料股份有限公司 | Catalyst for synthesizing acetonitrile and preparation method thereof |
| CN110252394B (en) * | 2019-07-18 | 2022-03-25 | 北京赛诺时飞石化科技有限公司 | Catalyst for preparing propylene oxide by propylene oxidation, preparation and application thereof |
| CN112808306A (en) * | 2021-01-13 | 2021-05-18 | 华东理工大学 | Preparation method and application of metal oxygen cluster catalyst with stable organic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| CN103896881A (en) * | 2012-12-24 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
-
2015
- 2015-10-14 CN CN201510660354.3A patent/CN106582807B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| CN103896881A (en) * | 2012-12-24 | 2014-07-02 | 中国石油化学工业开发股份有限公司 | Process for producing epoxide |
Non-Patent Citations (2)
| Title |
|---|
| "氧化镁改性微米TS-1催化丙烯环氧化";李俊平，等;《石油学报（石油加工）》;20120630;第28卷(第3期);第388-392页 |
| "钛硅分子筛的成型、表征及催化丙烯环氧化性能的研究";陈涛;《中国优秀硕博士学位论文全文数据库 (硕士) 工程科技I辑》;20020615;摘要、第14、23-24、27-37页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582807A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105854933B (en) | A kind of modifying titanium-silicon molecular sieve and its method of modifying and application | |
| CN106582807B (en) | Modifying titanium-silicon molecular sieve and method of modifying and the application in propylene ring oxidation reaction | |
| CN103708494B (en) | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve | |
| CN101327934B (en) | Preparation of titanium silicon molecular sieve having MFI structure | |
| CN110203947B (en) | Preparation method of titanium-silicon molecular sieve Ti-MWW | |
| CN103896302B (en) | A kind of si molecular sieves and preparation method thereof | |
| CN103864093A (en) | Stepped-type crystallization preparation method of titanium-containing molecular sieve | |
| CN106986351B (en) | A kind of synthetic method of titanium-silicon molecular sieve TS-1 and its application in propylene ring oxidation reaction | |
| CN104119300B (en) | A kind of method that australene epoxidation prepares 2,3-epoxypinane | |
| CN106587091B (en) | Preparation method containing continuous mesoporous Jie's micropore compound titanium silicon molecular sieve TS-1 | |
| CN106517236A (en) | Preparation method of titanium silicalite molecular sieve | |
| CN106115732A (en) | A kind of modifying titanium-silicon molecular sieve and method of modifying thereof and application | |
| CN104028300B (en) | Modified TS-1 molecular sieve as well as preparation method and application thereof | |
| CN110498778B (en) | Method for preparing cyclohexene oxide by epoxidation of cyclohexene | |
| CN108395370B (en) | Method for preparing benzaldehyde by oxidizing styrene | |
| CN103183356B (en) | Method for modifying titanium silicalite molecular sieve by precious metal source | |
| CN110372536B (en) | Method for preparing cyclohexanone oxime by cyclohexanone ammoximation | |
| CN103408434B (en) | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step | |
| CN109746041B (en) | Modification method of Ti-MWW molecular sieve and preparation method of cyclododecanone oxime | |
| CN107879897B (en) | One-step method for synthesizing o-diol compound | |
| CN110639602B (en) | Catalyst for producing monoethanolamine and diethanolamine | |
| CN110590580B (en) | Preparation method of monoethanolamine and diethanolamine | |
| CN108722498A (en) | A kind of cyclohexanone catalyst by cyclohexanol dehydrogenation support preparation method and application | |
| CN110642727B (en) | Method for increasing production of monoethanolamine and diethanolamine | |
| CN110642729B (en) | Method for synthesizing monoethanolamine and diethanolamine |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190418 Address after: 274500 Dongming County Chemical Park in Heze, Shandong Patentee after: Zhonghai environmental protection material Co Ltd Address before: 116023 Liaoning Dalian pun Wan New Area Pine Island Chemical Industrial Park Patentee before: DALIAN HETEROGENEOUS CATALYST CO., LTD. |
|
| TR01 | Transfer of patent right |