CN110252394A - A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation - Google Patents
A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation Download PDFInfo
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- CN110252394A CN110252394A CN201910650137.4A CN201910650137A CN110252394A CN 110252394 A CN110252394 A CN 110252394A CN 201910650137 A CN201910650137 A CN 201910650137A CN 110252394 A CN110252394 A CN 110252394A
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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
- 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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- 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
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- 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
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Abstract
The invention belongs to catalyst preparation technical fields, and in particular to a kind of catalyst and its preparation, application that propylene oxide is prepared for propylene oxidation.The modifying titanium-silicon molecular sieve film catalyst is the area load Ti-Si molecular sieve membrane using aluminium oxide as carrier, wherein the Ti-Si molecular sieve membrane surface is also loaded P2O5.The modifying titanium-silicon molecular sieve film catalyst has the characteristics that effective ratio area is big, catalyst activity is high, catalyst stability is good, in H2O2More effective active phase TiOO-H (HPO are produced in system4), there are the activity of catalyst and stability than existing titanium-silicon molecular sieve catalyst and Titanium Sieve Molecular Sieve film catalyst and is obviously improved.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of to prepare urging for propylene oxide for propylene oxidation
Agent and its preparation, application.
Background technique
Propylene oxide, alias methyl oxirane or propylene oxide (PO) are important three big basic organic chemical industry synthesis
One of raw material, yield and consumption figure are only second to polypropylene, are the second largest derivatives of propylene, mainly for the production of polyether polyols
Alcohol, and then generating polyurethane is processed, the application field of polyurethane is related to basic industry, national defence, the various aspects of people's daily life.
Can be used for the chemical industry substances such as production propylene glycol, propylene glycol and nonionic surfactant, fire retardant, automobile, building,
The industries such as food, tobacco, medicine and cosmetics have a wide range of applications.Therefore, research and development is efficient, economy, environment-friendly type
Synthesis of Propylene Oxide and catalyst have great importance.
PO industrialized preparing process is mainly chlorohydrination, conjugated oxidation on our times, oxygen direct oxidation method and peroxide
Change hydrogen direct oxidation method (HPPO method).Wherein chlorohydrination consumes a large amount of chlorine because of its production process, severe corrosion to equipment, together
When influence of the chlorine-contained wastewater to environment it is big the features such as, gradually substituted by new process.The characteristics of conjugated oxidation is industrial stream
Journey is long, investment is huge, and product category is more, and the price and the market demand of byproduct directly affect the benefit of whole PO.Oxygen
Direct oxidation method has obtained extensive research as the emerging means for preparing propylene oxide, but its industrial applications is less,
Still in phase of basic research.
HPPO sources of law from Enichem company, Italy using TS-1 as catalyst, by oxidant of hydrogen peroxide progress epoxidation
The production process of reaction.This method is that direct oxidation reaction prepares propylene oxide in fixed bed reactors, and reaction condition compares
Mildly, since the advent of the world has just obtained favorable comment.The technique overcomes chlorohydrination equipment seriously corroded, the disadvantage more than waste liquid, waste residue,
Industrial flow is simple, and product yield is high, and production process only generates propylene oxide and water, not the product of coproduction, " three wastes " discharge
Lack, raw material and auxiliary addition agent can be recycled, and infrastructure expense is low, and not only energy consumption low pollution is small, and industry chemical conversion
It is ripe, large-scale application has been obtained, presents good prospect.
US4410501 makes public for the first time the synthetic method of TS-1 molecular sieve, and US7378536, US7449590 are the special of representative
Benefit discloses one kind under titanium-silicon molecular sieve catalyst existence condition, and in the presence of methanol solvate, uses hydrogen peroxide system
The method of standby propylene oxide.But it is simple using Titanium Sieve Molecular Sieve as catalyst, by TS-1 molecular sieve reference area and hole
The influence of diameter, the conversion ratio of propylene and the selectivity of PO are all relatively low, and the stability of catalyst is also relatively poor.
The prior art also discloses the further improvement to such catalyst.As US3923843 and US4367342 are disclosed
The catalyst of the carrier loaded titanium of amorphous silica is used to prepare propylene oxide.But due to the ratio table of amorphous silica
Area and Kong Rongtai are small, therefore the content of Ti is difficult to improve, and affect the activity and stability of catalyst.United States Patent (USP)
A kind of method that US4701428 reports spray drying process preparation Titanium Sieve Molecular Sieve, however the catalyst granules of this method is only
20 microns, it is difficult in fixed bed reactors.
CN1268400A discloses a kind of using Titanium Sieve Molecular Sieve as catalyst activity component, mixed with aluminium oxide,
Extrusion or compression molding enable the particle of catalyst to be set according to the needs of commercial fixed bed reactor.Vinegar is used simultaneously
Hydrochlorate is handled, and the overall activity of catalyst is improved, at 40 DEG C of reaction temperature, reflect pressure 0.4MPa under the conditions of with hydrogen peroxide
Reaction, H2O2 conversion ratio reach 93.4%, and the selectivity of propylene oxide is up to 95.7%.
CN102822158A discloses a kind of by the pretreated method progress catalyst of TS-1 molecular sieve progress methanol solution
Preparation, be no longer additionally added methanol in industrial application, and the activity of the activity of catalyst and same addition methanol solvate
It is equivalent.Therefore, the activity and stability of catalyst are all relatively weak.
It is described in US8785670B2 and WO2012076543A1 patent and a kind of adds specific phosphorous contain in feed stream
Oxygen acid potassium salt effectively improves the technology of H2O2 conversion ratio and PO selectivity.Using the technique H2O2 total conversion >=
The purity of 99.8%, PO reach >=99.99%.But influenced by specific surface area of catalyst and Kong Rong, the entirety of catalyst is steady
It is qualitative relatively weak.
Meanwhile in past 15 years, there is lot of documents to carry out research report to Ti-Si molecular sieve membrane, such as
CN100999324A,CN101003012A.Compared to Titanium Sieve Molecular Sieve, Ti-Si molecular sieve membrane has high-fire resistance, high mechanical strength
And high chemical stability, there is important research significance in Membrane catalysis and UF membrane field.Titanium Sieve Molecular Sieve is on the porous material
Crystallization growth can be used for effective catalyst, be efficiently catalyzed a series of H with synthesis of titanium silicon molecular sieve film2O2The organic oxygen of participation
Change reaction.
Research in the reaction of propylene oxide is prepared for propylene oxidation however, yet there are no related Ti-Si molecular sieve membrane
With application;Moreover, being found in concrete practice, existing Ti-Si molecular sieve membrane is directlyed adopt as propylene oxidation and prepares epoxy third
When the catalyst of alkane, activity and stability are not very ideal.
Summary of the invention
In order to overcome the above technical problems, the present invention provides a kind of modifying titanium-silicon molecular sieve film catalyst.The Modified Titanium
Si molecular sieves film catalyst has the characteristics that effective ratio area is big, catalyst activity is high, catalyst stability is good.
Modifying titanium-silicon molecular sieve film catalyst of the present invention, using aluminium oxide as carrier, area load Titanium Sieve Molecular Sieve
Film, wherein further loading P in the Titanium Sieve Molecular Sieve film surface2O5。
The present invention carries out P Modification by matrix of Ti-Si molecular sieve membrane/alumina support, and the Ti-Si molecular sieve membrane can
It is well dispersed in alumina carrier surface, overcomes that existing Titanium Sieve Molecular Sieve specific surface area is small, defect of Kong Rong little;Gained catalysis
Agent has biggish Kong Rong, thus is remarkably improved its effective ratio area and catalytic activity bit quantity.Meanwhile the present invention passes through
To the P Modification of Ti-Si molecular sieve membrane, the effective active of catalyst Ti can be improved, and then in H2O2Generating in system more has
Imitate activity phase TiOO-H (HPO4), the activity and stability for finally making catalyst are than existing titanium-silicon molecular sieve catalyst and titanium silicon
Molecular sieve film catalyst, which has, to be obviously improved.
In the modifying titanium-silicon molecular sieve film catalyst, the P2O5Mass fraction be 0.1~3wt%, preferably 1~
2.5wt% can match within this range and generate optimal reactive intermediate, improve the activity and stability of catalyst.
In the modifying titanium-silicon molecular sieve film catalyst, mass fraction shared by the Ti-Si molecular sieve membrane be 10~
40wt%, preferably 20~30wt%.Gained catalyst has better catalytic activity and stability within this range.
The aluminium oxide is selected from γ-Al2O3, preferably specific surface area is 180~250m20.41~0.80ml/g of/g, Kong Rongwei
γ-Al2O3.It is more advantageous to load and the P of Titanium Sieve Molecular Sieve with biggish specific surface area and big hole Rong Tedian2O5's
Uniform load achievees the effect that active sites high degree of dispersion.
The present invention also provides the preparation methods of above-mentioned catalyst, comprising: uses equi-volume impregnating, utilizes phosphorous modifying agent
To load Ti-Si molecular sieve membrane alumina support be modified, dry, roasting to get.
The phosphorous modifying agent is selected from one of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate or several
Kind, preferably potassium dihydrogen phosphate;The study found that catalyst stability can be made to be further enhanced using potassium dihydrogen phosphate modification.
The temperature of the drying is 100-140 DEG C, preferably 120-130 DEG C;The study found that can make to contain phosphatization with this condition
It closes that object is more uniform is dispersed in catalyst surface, to further promote the specific surface area of catalyst, improves the activity of catalyst
And stability.
The temperature of the roasting is 400-600 DEG C, preferably 550-560 DEG C;Experiment shows gained catalyst with this condition
Acid function it is best.
As one of the preferred embodiment of the present invention, the alumina support of the load Ti-Si molecular sieve membrane changes through dipping
Property after, in 120 DEG C drying for 24 hours, 550 DEG C of roasting 4h to get.
The alumina support of load Ti-Si molecular sieve membrane of the present invention can be used conventional method in that art and be made, and such as will
Silicon source, titanium source, template and water mixing, are added alumina support, and crystallization filters, dry, roasting to get.
One of preferably, following methods system can be used in the alumina support of the load Ti-Si molecular sieve membrane
: using tetrapropylammonium hydroxide (TPAOH) as template, using tetraethyl orthosilicate as silicon source, using butyl titanate as titanium source,
After crystallization after filtering and washing to neutrality, dry 12h is placed in 80 DEG C of drying box, and finally 550 DEG C of roastings 6 are small in Muffle furnace
When to get.
The present invention also provides application of the above-mentioned modifying titanium-silicon molecular sieve film catalyst in HPPO method, be preferred for
H2O2It is prepared in the reaction of propylene oxide for oxidant by propylene, produces the active phase of more TiOO-H (HPO4), improve catalysis
The activity of agent.
The present invention also provides a kind of propylene in H2O2The method that oxidation reaction generates propylene oxide in system, comprising: will be above-mentioned
After modifying titanium-silicon molecular sieve film catalyst is packed into fixed bed reactors, enter reactor after propylene, methanol and hydrogen peroxide mixing,
On catalyst bed, epoxidation reaction occurs for propylene and hydrogen peroxide, generates the mixing containing propylene, propylene oxide, first alcohol and water
Solution;Wherein, the temperature of the reaction is 80~160 DEG C;Pressure is 1.5~3.5MPa, and Feed space velocities are 3.0~6.0h-1;Third
Alkene/hydrogen peroxide molar ratio 1.0~3.0.Experiment shows to be remarkably improved H using catalyst of the present invention2O2Conversion
The yield of rate, the selectivity of PO and PO.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment provides a kind of preparations of modifying titanium-silicon molecular sieve film catalyst, comprising:
(1) configuration tetrapropylammonium hydroxide (TPAOH) solution becomes SiO according to mol ratio group as template2:
TiO2:TPAOH:H2The preparation of O=1.0:0.03:0.18:18 progress Ti-Si molecular sieve membrane:
TPAOH (20wt%) and water are mixed to form to the solution A for being 10.62% containing TPAOH mass fraction first, simultaneously
According to SiO2:TiO2The ratio of=1.0:0.03 is chosen tetraethyl orthosilicate (silicon source) and is mixed with butyl titanate (titanium source)
Form solution B.Then solution B is slowly added into solution A and after stirring 30min, uniformly mixed solution is placed in 50 DEG C
Lower hydrolysis simultaneously carries out catching up with alcohol to clarification;Then a certain amount of aluminium oxide (Titanium Sieve Molecular Sieve account for total catalyst levels 10%) is added
Into solution, and crystallization 2 days in the homogeneous reaction kettle containing polytetrafluoroethyllining lining.
After obtained Ti-Si molecular sieve membrane/alumina support is carried out filtering and washing to neutrality, it is placed in 80 DEG C of drying box
Middle dry 12h, finally in Muffle furnace 550 DEG C roast 6 hours, finally obtaining containing Titanium Sieve Molecular Sieve mass fraction is 10%
Ti-Si molecular sieve membrane/alumina support A.
(2) the carrier A for weighing the quality such as two parts, using the water of the potassium dihydrogen phosphate of equi-volume impregnating dipping various concentration
Solution obtains load P2O5Equivalent percentage composition is respectively 1%, 2% catalyst, then naturally dry, 120 DEG C drying for 24 hours,
550 DEG C of roasting 4h, the number for finally preparing catalyst is respectively A1/A2.
Embodiment 2
The present embodiment provides a kind of preparations of modifying titanium-silicon molecular sieve film catalyst, comprising:
(1) according to the preparation method of embodiment 1, by adjusting the mass ratio of Ti-Si molecular sieve membrane and alumina support, system
Standby Ti-Si molecular sieve membrane/alumina support the B for being out 20% containing Titanium Sieve Molecular Sieve mass fraction.
(2) carrier B for weighing the quality such as two parts, using the water of the potassium dihydrogen phosphate of equi-volume impregnating dipping various concentration
Solution obtains P2O5Equivalent percentage composition is respectively 1%, 2% catalyst, then naturally dry, 120 DEG C drying for 24 hours, 550 DEG C
4h is roasted, the number for finally preparing catalyst is respectively B1/B2.
Embodiment 3
The present embodiment provides a kind of preparations of modifying titanium-silicon molecular sieve film catalyst, comprising:
(1) according to the preparation method of embodiment 1, by adjusting the mass ratio of Ti-Si molecular sieve membrane and alumina support, system
Standby Ti-Si molecular sieve membrane/alumina support the C for being out 30% containing Titanium Sieve Molecular Sieve mass fraction.
(2) support C for weighing the quality such as two parts, using the water of the potassium dihydrogen phosphate of equi-volume impregnating dipping various concentration
Solution obtains P2O5Equivalent percentage composition is respectively 1%, 2% catalyst, then naturally dry, 120 DEG C drying for 24 hours, 550 DEG C
4h is roasted, the number for finally preparing catalyst is respectively C1/C2.
Embodiment 4
The present embodiment provides a kind of preparations of modifying titanium-silicon molecular sieve film catalyst, comprising:
(1) according to the preparation method of embodiment 1, by adjusting the mass ratio of Ti-Si molecular sieve membrane and alumina support, system
Standby Ti-Si molecular sieve membrane/alumina support the D for being out 40% containing Titanium Sieve Molecular Sieve mass fraction.
(2) the carrier D for weighing the quality such as two parts, using the water of the potassium dihydrogen phosphate of equi-volume impregnating dipping various concentration
Solution obtains P2O5Equivalent percentage composition is respectively 1%, 2% catalyst, then naturally dry, 120 DEG C drying for 24 hours, 550 DEG C
4h is roasted, the number for finally preparing catalyst is respectively D1/D2.
Comparative example 1
Using the carrier A/B/C/D that is prepared in embodiment 1-4 as comparative catalyst, i.e., without solution containing phosphate
Modified Titanium Sieve Molecular Sieve film catalyst.
Comparative example 2
With the Titanium Sieve Molecular Sieve for preparing according to the method for embodiment 1 catalyst E as a comparison, i.e., do not used in embodiment 1
Titanium Sieve Molecular Sieve obtained from alumina support.
The evaluation of catalyst
Method is as follows:
Take above 8 kinds of n-alkane low temperature isomerization catalyst (Cat A1, Cat A2, Cat B1, Cat B2, Cat C1,
It is anti-that Cat C2, Cat D1, Cat D2 and comparative catalyst Cat A, Cat B, Cat C, Cat D, Cat E are respectively charged into fixed bed
After answering device, propylene, methanol and hydrogen peroxide enter reactor, propylene and dioxygen on catalyst bed after the mixing of reactor stage
Water occur epoxidation reaction, generate containing propylene, propylene oxide, first alcohol and water mixed solution.
Catalyst bed reaction temperature is 140 DEG C, pressure 2.1MPa, Feed space velocities 3.0-6.0h-1, propylene/dioxygen
Water molar ratio 2.0.
The content that hydrogen peroxide is surveyed with potentiometric titration, with the content of other organic matters of coefficients data measured by chromatography.
Its calculation formula is as follows:
Data processing:
Hydrogen peroxide conversion ratio=consumption H2O2Amount/H2O2Initial amount
H consumed by propylene oxide selectivity=generation PO2O2Amount/H2O2The amount of consumption
Propylene oxide yield=hydrogen peroxide conversion ratio * propylene oxide selectivity
The results are shown in Table 1 for final evaluating catalyst.
1 catalyst performance evaluation result of table:
Catalyst number | H2O2Conversion ratio, wt% | PO selectivity, wt% | PO yield, % |
Cat A1 | 93.1 | 88.7 | 82.6 |
Cat A2 | 94.2 | 90.1 | 84.9 |
Cat B1 | 96.4 | 94.1 | 90.7 |
Cat B2 | 97.1 | 95.2 | 92.4 |
Cat C1 | 96.8 | 94.5 | 91.5 |
Cat C2 | 97.5 | 96.5 | 94.1 |
Cat D1 | 92.5 | 89.6 | 82.9 |
Cat D2 | 93.3 | 90.1 | 84.1 |
Compare Cat A | 85.1 | 83.5 | 71.1 |
Compare Cat B | 84.6 | 84.1 | 71.1 |
Compare Cat C | 86.6 | 85.3 | 73.9 |
Compare Cat D | 85.6 | 83.2 | 71.2 |
Compare Cat E | 84.5 | 82.3 | 69.5 |
It can be seen that the catalyst that embodiment 1-4 is obtained by the response data in contrast table 1 to be catalyzed compared to comparative example
Agent H with higher2O2Conversion ratio, PO selectivity and PO yield, wherein the performance of catalyst B2 and C2 is best.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of modifying titanium-silicon molecular sieve film catalyst, using aluminium oxide as carrier, area load Ti-Si molecular sieve membrane, feature exists
In the Ti-Si molecular sieve membrane area load P2O5。
2. modifying titanium-silicon molecular sieve film catalyst according to claim 1, which is characterized in that the P2O5Mass fraction
For 0.1~3wt%, preferably 1~2.5wt%.
3. modifying titanium-silicon molecular sieve film catalyst according to claim 1 or 2, which is characterized in that the Titanium Sieve Molecular Sieve
Mass fraction shared by film is 10~40wt%, preferably 20~30wt%.
4. modifying titanium-silicon molecular sieve film catalyst according to claim 1 to 3, which is characterized in that the aluminium oxide choosing
From γ-Al2O3;Preferably, it is 180~250m that the aluminium oxide, which is selected from specific surface area,20.41~0.80ml/g's of/g, Kong Rongwei
γ-Al2O3。
5. the preparation method of any modifying titanium-silicon molecular sieve film catalyst of claim 1-4 characterized by comprising
Using equi-volume impregnating, it is modified, is dried, roasting using alumina support of the phosphorous modifying agent to load Ti-Si molecular sieve membrane
Burn to get.
6. preparation method according to claim 5, which is characterized in that the phosphorous modifying agent is selected from phosphoric acid, phosphoric acid hydrogen two
One or more of ammonium, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, preferably potassium dihydrogen phosphate.
7. preparation method according to claim 5 or 6, which is characterized in that the temperature of the drying is 100-140 DEG C, excellent
Select 120-130 DEG C;
And/or the temperature of the roasting is 400-600 DEG C, preferably 550-560 DEG C.
8. according to any preparation method of claim 5-7, which is characterized in that using tetrapropylammonium hydroxide as template
Agent, using tetraethyl orthosilicate as silicon source, using butyl titanate as titanium source.
9. -4 any modifying titanium-silicon molecular sieve film catalysts are in HPPO method with H according to claim 12O2It is oxidant by third
Alkene is prepared in the reaction of propylene oxide and is applied.
10. a kind of propylene is in H2O2The method that oxidation reaction generates propylene oxide in system characterized by comprising right
After asking any modifying titanium-silicon molecular sieve film catalyst of 1-4 to be packed into fixed bed reactors, after propylene, methanol and hydrogen peroxide mixing
Into reactor, on catalyst bed, epoxidation reaction occurs for propylene and hydrogen peroxide, generates and contains propylene, propylene oxide, first
The mixed solution of alcohol and water;Wherein, the temperature of the reaction is 80~160 DEG C;Pressure is 1.5~3.5MPa, and Feed space velocities are
3.0~6.0h-1;Propylene/hydrogen peroxide molar ratio 1.0~3.0.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110947375A (en) * | 2019-11-26 | 2020-04-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene oxide and preparation method thereof |
CN114345405A (en) * | 2021-12-28 | 2022-04-15 | 万华化学集团股份有限公司 | Load-forming titanium-silicon molecular sieve, preparation method thereof, and preparation method of benzenediol |
CN115745919A (en) * | 2022-10-20 | 2023-03-07 | 中国科学院大连化学物理研究所 | Synthesis method of propylene oxide |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1985004855A1 (en) * | 1984-04-26 | 1985-11-07 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions |
US4801309A (en) * | 1984-04-13 | 1989-01-31 | Uop | Titanium-aluminum-phosphorus-silicon-oxide molecular sieves |
CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
CN101003012A (en) * | 2006-12-27 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing novel catalytic film reactor |
WO2007092216A2 (en) * | 2006-02-07 | 2007-08-16 | Celanese International Corporation | Oxidation catalyst |
CN101774615A (en) * | 2010-01-20 | 2010-07-14 | 吉林大学 | Preparation method for spherical aluminum trioxide catalyst carrier |
CN102530982A (en) * | 2012-01-09 | 2012-07-04 | 河北科技大学 | Method for preparing titanium silicalite film by dynamic in-situ hydrothermal method |
CN103037967A (en) * | 2010-05-17 | 2013-04-10 | 科学设计公司 | Method for preparing an epoxidation catalyst |
CN103204830A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Catalytic oxidation method of styrene |
CN103708494A (en) * | 2013-12-26 | 2014-04-09 | 中国天辰工程有限公司 | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve |
CN105461661A (en) * | 2014-09-29 | 2016-04-06 | 中国石油化工股份有限公司 | Olefin oxidation method |
CN106083199A (en) * | 2016-06-24 | 2016-11-09 | 江西师范大学 | Method for preparing Ti-MWW molecular sieve membrane |
CN106390994A (en) * | 2016-08-31 | 2017-02-15 | 南京禾宇化工有限公司 | Catalyst taking aluminum oxide as carrier |
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 |
CN108654682A (en) * | 2017-03-31 | 2018-10-16 | 中国石油化工股份有限公司 | It is a kind of to load the multistage pore canal composite material and preparation method for having TS-1 zeolite membranes |
CN109433259A (en) * | 2018-10-31 | 2019-03-08 | 中海油天津化工研究设计院有限公司 | A kind of method of in-situ modified oxidation catalyst of cyclopropene |
-
2019
- 2019-07-18 CN CN201910650137.4A patent/CN110252394B/en active Active
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801309A (en) * | 1984-04-13 | 1989-01-31 | Uop | Titanium-aluminum-phosphorus-silicon-oxide molecular sieves |
WO1985004855A1 (en) * | 1984-04-26 | 1985-11-07 | Union Carbide Corporation | Titanium-aluminum-silicon-oxide molecular sieve compositions |
CN1418876A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Catalyst for olefine epoxidation |
CN1900071A (en) * | 2005-07-21 | 2007-01-24 | 中国科学院大连化学物理研究所 | Process for preparing epoxy chloropropane |
WO2007092216A2 (en) * | 2006-02-07 | 2007-08-16 | Celanese International Corporation | Oxidation catalyst |
CN101003012A (en) * | 2006-12-27 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing novel catalytic film reactor |
CN101774615A (en) * | 2010-01-20 | 2010-07-14 | 吉林大学 | Preparation method for spherical aluminum trioxide catalyst carrier |
CN103037967A (en) * | 2010-05-17 | 2013-04-10 | 科学设计公司 | Method for preparing an epoxidation catalyst |
CN102530982A (en) * | 2012-01-09 | 2012-07-04 | 河北科技大学 | Method for preparing titanium silicalite film by dynamic in-situ hydrothermal method |
CN103204830A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Catalytic oxidation method of styrene |
CN103708494A (en) * | 2013-12-26 | 2014-04-09 | 中国天辰工程有限公司 | Novel modification method of titanium silicalite molecular sieve and application of titanium silicalite molecular sieve |
CN105461661A (en) * | 2014-09-29 | 2016-04-06 | 中国石油化工股份有限公司 | Olefin oxidation method |
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 |
CN106083199A (en) * | 2016-06-24 | 2016-11-09 | 江西师范大学 | Method for preparing Ti-MWW molecular sieve membrane |
CN106390994A (en) * | 2016-08-31 | 2017-02-15 | 南京禾宇化工有限公司 | Catalyst taking aluminum oxide as carrier |
CN108654682A (en) * | 2017-03-31 | 2018-10-16 | 中国石油化工股份有限公司 | It is a kind of to load the multistage pore canal composite material and preparation method for having TS-1 zeolite membranes |
CN109433259A (en) * | 2018-10-31 | 2019-03-08 | 中海油天津化工研究设计院有限公司 | A kind of method of in-situ modified oxidation catalyst of cyclopropene |
Non-Patent Citations (5)
Title |
---|
JIAO, WY ET AL.: ""Ti-rich TS-1: A highly active catalyst for epoxidation of methallyl chloride to 2-methyl epichlorohydrin"", 《APPLIED CATALYSIS A: GENERAL》 * |
KHAZAEI, A ET AL.: ""Highly Efficient Etherification and Oxidation of Aromatic Alcohols Using Supported and Unsupported Phosphorus Pentoxide as a Heterogeneous Reagent"", 《SYNTHETIC COMMUNICATIONS》 * |
WANG, XD ET AL.: ""Synthesis of b-oriented TS-1 films on chitosan-modiried alpha-Al2O3 substrates"", 《ADVANCED MATERIALS》 * |
瞿丽文等: ""钛硅分子筛的改性:文献综述"", 《广东化工》 * |
陈晓晖等: ""钛硅分子筛膜的合成及其催化性能的研究"", 《化工进展》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110947375A (en) * | 2019-11-26 | 2020-04-03 | 红宝丽集团股份有限公司 | Catalyst for preparing propylene oxide and preparation method thereof |
CN114345405A (en) * | 2021-12-28 | 2022-04-15 | 万华化学集团股份有限公司 | Load-forming titanium-silicon molecular sieve, preparation method thereof, and preparation method of benzenediol |
CN114345405B (en) * | 2021-12-28 | 2023-09-19 | 万华化学集团股份有限公司 | Load-formed titanium-silicon molecular sieve and preparation method thereof, and preparation method of benzenediol |
CN115745919A (en) * | 2022-10-20 | 2023-03-07 | 中国科学院大连化学物理研究所 | Synthesis method of propylene oxide |
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