CN105854933B - A kind of modifying titanium-silicon molecular sieve and its method of modifying and application - Google Patents
A kind of modifying titanium-silicon molecular sieve and its method of modifying and application Download PDFInfo
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- CN105854933B CN105854933B CN201610453635.6A CN201610453635A CN105854933B CN 105854933 B CN105854933 B CN 105854933B CN 201610453635 A CN201610453635 A CN 201610453635A CN 105854933 B CN105854933 B CN 105854933B
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- 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
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- 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
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- 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
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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Abstract
The invention discloses a kind of modifying titanium-silicon molecular sieve and its method of modifying and applications, first nitrate and water are uniformly mixed and are prepared into nitrate aqueous solution, then molding strip Titanium Sieve Molecular Sieve is impregnated in nitrate aqueous solution, it is filtered after 1~72h of dipping, after obtained solid is dried at 80~120 DEG C, to get modifying titanium-silicon molecular sieve after 4~12h of roasting at 500~550 DEG C.The skeleton structure of modifying titanium-silicon molecular sieve is without substantially changeing, but due to the mutual synergistic effect of metal oxide and Titanium Sieve Molecular Sieve, make it that can significantly reduce the decomposition of hydrogen peroxide in propylene ring oxidation reaction, can effectively improve the effective rate of utilization of hydrogen peroxide.Modifying titanium-silicon molecular sieve is used for using methanol in the liquid propylene epoxidation reaction of solvent, the decomposition to hydrogen peroxide to be reduced, to improve the effective rate of utilization of its hydrogen peroxide in propylene ring oxidation reaction.
Description
Technical field
The present invention relates to a kind of method of modifying of Titanium Sieve Molecular Sieve, modified Titanium Sieve Molecular Sieve can be used for methanol being molten
In the liquid propylene epoxidation reaction of agent, belong to technical field of inorganic.
Background technology
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 structures identical with ZSM-5 molecular sieve.Due to transition gold
The introducing for belonging to titanium makes TS-1 be 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 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 for 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 shortcomings of active low and selectivity of product is poor, simultaneously because being led 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 danger of Chemical Manufacture.Therefore people constantly change and are 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.
Patent CN 200410089349.3 discloses a kind of preparation method of sour modifying titanium-silicon molecular sieve, by what is do not roasted
Titanium Sieve Molecular Sieve original powder is uniformly mixed with the solution of inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid), and acid is carried out at 60~160 DEG C
Processing 5~24 hours.Patent CN 99126289.1 proposes a kind of organic base (such as fatty amines, alcamines, quaternary ammonium bases
Close object) method that TS-1 is modified, this method be Titanium Sieve Molecular Sieve and organic base mixture are put into crystallizing kettle in 120~
It is handled 5~240 hours at 200 DEG C.Patent CN 200410021037.9 uses the nitrate or acetic acid of copper, lead, cobalt, nickel, silver etc.
The aqueous solution of salt is modified Titanium Sieve Molecular Sieve.Patent CN 201110451762.X use as Ru, R hours, Pd, Re, Os,
Ir, Pt, Au noble metal source and such as tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, n-propylamine, hexamethylene diamine organic alkali solution are mixed
It is handled at least 2 hours at 100~200 DEG C in closed reaction kettle after conjunction, to improve it applied in propylene ring oxidation reaction
Activity with selectivity.Patent CN 201010558620.9 is using soluble magnesium salt (such as magnesium sulfate, magnesium chloride) and soluble aluminum
Salt (such as aluminium chloride, aluminum sulfate, aluminum nitrate) is modified Titanium Sieve Molecular Sieve, so as to soda acid possessed by magnesium or aluminum material
The oxidation effect of effect and Titanium Sieve Molecular Sieve acts synergistically so that the choosing of hydroquinone is improved in phenol hydroxylation reaction process
Selecting property.Above in modified method, processing is modified to Titanium Sieve Molecular Sieve using organic base or acid, there is certain corruption to equipment
Corrosion, processing procedure is cumbersome, and the waste water discharged is also required to neutralisation treatment.Processing is modified using precious metal salt, by
In having used precious metal raw material, therefore processing cost is higher.
Invention content
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 modified it by metal salt solution strip Titanium Sieve Molecular Sieve after molding, is separated by solid-liquid separation operation
It is very simple.
It is a kind of by the modified obtained modifying titanium-silicon molecular sieve of the above method the second object of the present invention is to provide, it is modified
Titanium Sieve Molecular Sieve makes it can be in propylene ring oxidation reaction due to the mutual synergistic effect of metal oxide and Titanium Sieve Molecular Sieve
The apparent decomposition for reducing hydrogen peroxide, can effectively improve the effective rate of utilization of hydrogen peroxide and the choosing of product propene oxide
Selecting property.
The third object of the present invention is to provide a kind of application of above-mentioned modifying titanium-silicon molecular sieve, for using methanol as solvent
In liquid propylene epoxidation reaction, the effective rate of utilization of its hydrogen peroxide in propylene ring oxidation reaction is improved.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of method of modifying of Titanium Sieve Molecular Sieve, includes the following steps：
First nitrate and water are uniformly mixed and are prepared into nitrate aqueous solution, then soaks molding strip Titanium Sieve Molecular Sieve
Stain filters in nitrate aqueous solution after impregnating 1~72h, after obtained solid dries 2~6h at 80~120 DEG C, then at
To get modifying titanium-silicon molecular sieve after 4~12h of roasting at 500~550 DEG C；
The mass ratio of the nitrate, water and molding strip Titanium Sieve Molecular Sieve is：0.001~0.5：0.1~5：1.
In above-mentioned technical proposal, the nitrate is barium nitrate, alternatively, barium nitrate and zinc nitrate and/or lanthanum nitrate are mixed
Mixture made of conjunction, barium nitrate, zinc nitrate, lanthanum nitrate mass ratio be 1：0~3.0：0~1.5；
Further, the barium nitrate, zinc nitrate, lanthanum nitrate mass ratio be preferably 1：0.2~2.0：0.1~1.0,
More preferably 1：0.5~2.0：0.3~1.0.
In above-mentioned technical proposal, the mass ratio of the nitrate, water and molding strip Titanium Sieve Molecular Sieve is preferably：
0.001~0.1：0.1~2：1.
In above-mentioned technical proposal, the dip time is preferably 12~48h.
In above-mentioned technical proposal, the molding strip Titanium Sieve Molecular Sieve is prepared by the following method：It will
The 20g Titanium Sieve Molecular Sieve original powders and 1 that conventionally (Zeolites, page 1992, Vol.12 the 943rd~950) is prepared
Gram field mountain valley with clumps of trees and bamboo powder after mixing, be added 14 milliliters of 30wt% Ludox further after mixing use banded extruder extrusion at
Type, by molding sample, drying roasts 6 hours strip Titanium Sieve Molecular Sieve to obtain the final product after 12 hours at 550 DEG C at 100 DEG C.
It is the modification obtained from being modified as above-mentioned method of modifying the present invention also provides a kind of modifying titanium-silicon molecular sieve
There is Titanium Sieve Molecular Sieve MFI structure, XRD spectrum to see Fig. 1.
The present invention also provides a kind of applications of above-mentioned modifying titanium-silicon molecular sieve, are used for using methanol as solvent as catalyst
In liquid propylene epoxidation reaction, which carries out in fixed-bed reactor, and reaction condition is：35~40 DEG C of temperature, pressure
2.5~3.0Mpa of power, 0.8~1.2h-1 of air speed of propylene, propylene and H2O2Molar ratio be 2~4：1.
The advantages of technical solution of the present invention, is：Titanium Sieve Molecular Sieve method of modifying of the present invention, operation is simple,
Simultaneously because the mutual synergistic effect of metal oxide and Titanium Sieve Molecular Sieve, makes it can be apparent in liquid propylene epoxidation reaction
Reduction hydrogen peroxide decomposition, can effectively improve the effective rate of utilization of hydrogen peroxide.
Description of the drawings
Fig. 1：The XRD spectrum of modifying titanium-silicon molecular sieve prepared by the embodiment of the present invention.
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but the present invention is not limited in being described below
Hold, the reagent used in embodiment is commercially available chemically pure reagent.
The strip Titanium Sieve Molecular Sieve used in following embodiment is prepared by the following method, first according to
Method described in " Zeolites, page 1992, Vol.12 the 943rd~950 " prepares Titanium Sieve Molecular Sieve original powder：With ethyl orthosilicate
For silicon source, butyl titanate is titanium source, and tetrapropylammonium hydroxide is template, in 150~200 DEG C of crystallization 12~48 hours, warp
Be filtered, washed, dry, roast after obtain Titanium Sieve Molecular Sieve original powder；20g Titanium Sieve Molecular Sieve original powder is mixed with 1 gram of field mountain valley with clumps of trees and bamboo powder
After uniformly, the Ludox that 14 milliliters of 30wt% are added further uses banded extruder extruded moulding after mixing, by molding sample
Drying roasts 6 hours up to strip Titanium Sieve Molecular Sieve, labeled as " control titanium silicon point at 550 DEG C at 100 DEG C after 12 hours
Son sieve ".
Embodiment 1：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：0.68 gram of barium nitrate is dissolved in 30 grams
It is uniformly mixed in ionized water and is prepared into nitrate aqueous solution, 30 grams of control Titanium Sieve Molecular Sieve are impregnated in nitrate aqueous solution,
Dipping filters afterwards for 24 hours, is roasted 6 hours then at 550 DEG C after solid is 4 hours dry at 100 DEG C, obtains modifying titanium-silicon molecular sieve,
The content that BaO in the molecular sieve is measured labeled as modifying titanium-silicon molecular sieve A, XRF is compare Titanium Sieve Molecular Sieve quality 0.49%；
There is modifying titanium-silicon molecular sieve MFI structure, XRD diagram to see Fig. 1.
Embodiment 2：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate and 1.46 gram six
Nitric hydrate zinc, which is dissolved in being uniformly mixed in 30 grams of deionized waters, is prepared into nitrate aqueous solution, by 30 grams of control Titanium Sieve Molecular Sieve leachings
In nitrate aqueous solution, dipping filters stain afterwards for 24 hours, is roasted 6 hours then at 550 DEG C after solid is 4 hours dry at 100 DEG C,
Modifying titanium-silicon molecular sieve is obtained, modifying titanium-silicon molecular sieve B is labeled as, the content that XRF measures BaO, ZnO in the molecular sieve is respectively
Compare 0.32%, the 0.57% of Titanium Sieve Molecular Sieve quality.
Embodiment 3：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate and 1.06 gram six
Nitric hydrate lanthanum, which is dissolved in being uniformly mixed in 30 grams of deionized waters, is prepared into nitrate aqueous solution, by 30 grams of control Titanium Sieve Molecular Sieve leachings
In nitrate aqueous solution, dipping filters stain afterwards for 24 hours, is roasted 6 hours then at 550 DEG C after solid is 4 hours dry at 100 DEG C,
Modifying titanium-silicon molecular sieve is obtained, BaO, La in the molecular sieve are measured labeled as modifying titanium-silicon molecular sieve C, XRF2O3Content difference
To compare 0.35%, the 0.66% of Titanium Sieve Molecular Sieve quality.
Embodiment 4：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate and 1.14 gram six
Nitric hydrate zinc, which is dissolved in being uniformly mixed in 30 grams of deionized waters, is prepared into nitrate aqueous solution, by 30 grams of control Titanium Sieve Molecular Sieve leachings
In nitrate aqueous solution, dipping filters stain afterwards for 24 hours, is roasted 6 hours then at 550 DEG C after solid is 4 hours dry at 100 DEG C,
Modifying titanium-silicon molecular sieve is obtained, modifying titanium-silicon molecular sieve D is labeled as, the content that XRF measures BaO, ZnO in the molecular sieve is respectively
Compare 0.41%, the 0.41% of Titanium Sieve Molecular Sieve quality.
Embodiment 5：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate and 0.52 gram six
Nitric hydrate lanthanum, which is dissolved in being uniformly mixed in 30 grams of deionized waters, is prepared into nitrate aqueous solution, by 30 grams of control Titanium Sieve Molecular Sieve leachings
In nitrate aqueous solution, dipping filters stain afterwards for 24 hours, is roasted 6 hours then at 550 DEG C after solid is 4 hours dry at 100 DEG C,
Modifying titanium-silicon molecular sieve is obtained, BaO, La in the molecular sieve are measured labeled as modifying titanium-silicon molecular sieve E, XRF2O3Content difference
To compare 0.35%, the 0.40% of Titanium Sieve Molecular Sieve quality.
Embodiment 6：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate, 1.46 gram of six water
It closes zinc nitrate and 1.06 grams of lanthanum nitrate hexahydrates is dissolved in being uniformly mixed in 30 grams of deionized waters and is prepared into nitrate aqueous solution, by 30
Gram control Titanium Sieve Molecular Sieve is impregnated in nitrate aqueous solution, and dipping filters afterwards for 24 hours, solid at 100 DEG C after dry 4 hours again
It is roasted 6 hours in 550 DEG C, obtains modifying titanium-silicon molecular sieve, measured in the molecular sieve labeled as modifying titanium-silicon molecular sieve F, XRF
BaO、ZnO、La2O3Content be respectively compare Titanium Sieve Molecular Sieve quality 0.30%, 0.47%, 0.52%.
Embodiment 7：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate, 1.14 gram of six water
It closes zinc nitrate and 0.52 gram of lanthanum nitrate hexahydrate is dissolved in being uniformly mixed in 30 grams of deionized waters and is prepared into nitrate aqueous solution, by 30
Gram control Titanium Sieve Molecular Sieve is impregnated in nitrate aqueous solution, and dipping filters afterwards for 24 hours, solid at 100 DEG C after dry 4 hours again
It is roasted 6 hours in 550 DEG C, obtains modifying titanium-silicon molecular sieve, measured in the molecular sieve labeled as modifying titanium-silicon molecular sieve G, XRF
BaO、ZnO、La2O3Content be respectively compare Titanium Sieve Molecular Sieve quality 0.41%, 0.33%, 0.28%.
Embodiment 8：
A kind of modifying titanium-silicon molecular sieve, is prepared by following methods：By 0.68 gram of barium nitrate, 0.57 gram of six water
It closes zinc nitrate and 0.21 gram of lanthanum nitrate hexahydrate is dissolved in being uniformly mixed in 30 grams of deionized waters and is prepared into nitrate aqueous solution, by 30
Gram control Titanium Sieve Molecular Sieve is impregnated in nitrate aqueous solution, and dipping filters afterwards for 24 hours, solid at 100 DEG C after dry 4 hours again
It is roasted 6 hours in 550 DEG C, obtains modifying titanium-silicon molecular sieve, measured in the molecular sieve labeled as modifying titanium-silicon molecular sieve H, XRF
BaO、ZnO、La2O3Content be respectively compare Titanium Sieve Molecular Sieve quality 0.52%, 0.20%, 0.13%.
Application Example：
The modifying titanium-silicon molecular sieve that control Titanium Sieve Molecular Sieve and embodiment 1-8 are obtained carries out experimental evaluation：Respectively by 3 grams
In the reaction tube for the stainless steel clamp set that catalyst sample is filled loaded on upper and lower ends with φ 3mm inertia glass marbles, in reaction process,
Maintenance reaction pressure is 3.0Mpa, and reaction temperature is 38 DEG C, and reactant hydrogen peroxide, propylene liguid and solvent methanol are by pumping simultaneously
It enters in reaction tube, the air speed of propylene is 0.8h-1, the molar ratio of propylene and hydrogen peroxide is 3：1, it periodically takes during the reaction
Sample is analyzed, and the results are shown in Table 1, wherein XH2O2、SPO、UH2O2Respectively represent H2O2Conversion ratio, propylene oxide selectivity and H2O2Have
Imitate utilization rate.
Table 1：The catalytic effect in liquid propylene epoxidation reaction of different Titanium Sieve Molecular Sieve
| Sample source | Catalyst is numbered | XH2O2(%) | SPO(%) | UH2O2(%) |
| Compare Titanium Sieve Molecular Sieve | 98.2 | 88.2 | 80.1 | |
| Embodiment 1 | Modifying titanium-silicon molecular sieve A | 97.9 | 94.6 | 88.2 |
| Embodiment 2 | Modifying titanium-silicon molecular sieve B | 97.7 | 99.5 | 87.9 |
| Embodiment 3 | Modifying titanium-silicon molecular sieve C | 97.8 | 99.2 | 86.8 |
| Embodiment 4 | Modifying titanium-silicon molecular sieve D | 98.3 | 98.0 | 90.0 |
| Embodiment 5 | Modifying titanium-silicon molecular sieve E | 98.1 | 98.5 | 92.7 |
| Embodiment 6 | Modifying titanium-silicon molecular sieve F | 90.2 | 99.2 | 85.3 |
| Embodiment 7 | Modifying titanium-silicon molecular sieve G | 98.0 | 98.8 | 96.7 |
| Embodiment 8 | Modifying titanium-silicon molecular sieve H | 98.4 | 98.0 | 94.8 |
As can be seen from the above table, barium monoxide, zinc oxide and the composite modified processing of lanthana are carried out to Titanium Sieve Molecular Sieve, it can be with
Significantly improve H during propylene ring oxidation reaction2O2Effective rate of utilization, while improving the selectivity of product propene oxide.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.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 (7)
1. a kind of method of modifying of Titanium Sieve Molecular Sieve, which is characterized in that include the following steps：
First nitrate and water are uniformly mixed and are prepared into nitrate aqueous solution, is then impregnated in molding strip Titanium Sieve Molecular Sieve
In nitrate aqueous solution, filtered after impregnating 1~72h, after obtained solid dries 2~6h at 80~120 DEG C, then at 500~
To get modifying titanium-silicon molecular sieve after 4~12h of roasting at 550 DEG C；
The mass ratio of the nitrate, water and molding strip Titanium Sieve Molecular Sieve is：0.001~0.5：0.1~5：1；
The nitrate is the mixture that barium nitrate, zinc nitrate, lanthanum nitrate mix, barium nitrate, zinc nitrate, lanthanum nitrate
Mass ratio is 1：0.2~2.0：0.1~1.0.
2. according to the method described in claim 1, it is characterized in that, the mass ratio of the barium nitrate, zinc nitrate, lanthanum nitrate is
1：0.5~2.0：0.3~1.0.
3. according to the method described in claim 1, it is characterized in that, the nitrate, water and molding strip titanium silicon molecule
The mass ratio of sieve is：0.001~0.1：0.1~2：1.
4. according to the method described in claim 1, it is characterized in that, the dip time is 12~48h.
5. according to the method described in claim 1, it is characterized in that, the molding strip Titanium Sieve Molecular Sieve is according to following
What method was prepared：The Titanium Sieve Molecular Sieve original powder that 20g is conventionally prepared is uniformly mixed with 1 gram of field mountain valley with clumps of trees and bamboo powder
Afterwards, the Ludox that 14 milliliters of 30wt% are added further uses banded extruder extruded moulding after mixing, by molding sample in 100
Drying roasts 6 hours up to strip Titanium Sieve Molecular Sieve at 550 DEG C at DEG C after 12 hours.
6. a kind of modifying titanium-silicon molecular sieve, which is characterized in that be modified by any one of Claims 1 to 5 method of modifying
Obtained from.
7. a kind of application of the modifying titanium-silicon molecular sieve described in claim 6, which is characterized in that be used for methanol as catalyst
For in the liquid propylene epoxidation reaction of solvent, which carries out in fixed-bed reactor, and reaction condition is：Temperature 35~
40 DEG C, 2.5~3.0MPa of pressure, 0.8~1.2h of air speed of propylene-1, propylene and H2O2Molar ratio be 2~4：1.
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| WO2018115117A1 (en) | 2016-12-20 | 2018-06-28 | Basf Se | A process for preparing an extrudable composition comprising a titanium-containing zeolitic material having framework type mww |
| WO2018134289A1 (en) * | 2017-01-18 | 2018-07-26 | Basf Se | A process for preparing a molding comprising zinc and a titanium-containing zeolite |
| CN106986351B (en) * | 2017-04-18 | 2019-05-24 | 中触媒新材料股份有限公司 | A kind of synthetic method of titanium-silicon molecular sieve TS-1 and its application in propylene ring oxidation reaction |
| CN110548539A (en) * | 2019-08-23 | 2019-12-10 | 江苏扬农化工集团有限公司 | Modification method of titanium silicalite molecular sieve catalyst for HPPO |
| KR20220113807A (en) | 2019-12-20 | 2022-08-16 | 바스프 에스이 | Moldings comprising Ti-MWW zeolite and having a specific Lewis acidity |
| CN111085265B (en) * | 2019-12-27 | 2021-04-23 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof |
| CN112791744B (en) * | 2020-12-22 | 2024-03-19 | 上海华峰新材料研发科技有限公司 | Modified titanium-silicon molecular sieve and preparation method and application thereof |
| CN115920958A (en) * | 2022-12-21 | 2023-04-07 | 中触媒新材料股份有限公司 | Modification method and application of titanium-silicon molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
| CN106582807A (en) * | 2015-10-14 | 2017-04-26 | 中触媒新材料股份有限公司 | Modified titanium-silicon molecular sieve, modification method and application thereof in propylene epoxidation reaction |
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| 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 |
| CN106582807A (en) * | 2015-10-14 | 2017-04-26 | 中触媒新材料股份有限公司 | Modified titanium-silicon molecular sieve, modification method and application thereof in propylene epoxidation reaction |
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