CN105524025B - A kind of method of oxyalkylene - Google Patents
A kind of method of oxyalkylene Download PDFInfo
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- CN105524025B CN105524025B CN201410514949.3A CN201410514949A CN105524025B CN 105524025 B CN105524025 B CN 105524025B CN 201410514949 A CN201410514949 A CN 201410514949A CN 105524025 B CN105524025 B CN 105524025B
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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
- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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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
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of method of oxyalkylene, it is included under oxidation reaction condition, make the liquid mixture containing alkene and at least one oxidant and Titanium Sieve Molecular Sieve haptoreaction in the reactor, wherein, when desirable oxidation selectivity of product is decreased below desired value, raises reaction temperature and alternatively improve the quality of oxidant in liquid mixture until desirable oxidation product meets desired value.This method can effectively extend the single trip use service life of the Titanium Sieve Molecular Sieve as catalyst, reduce the regeneration frequency of catalyst, while production efficiency is improved, it is possible to increase operation stability, extends the terminal life of catalyst.
Description
Technical field
The present invention relates to a kind of method of oxyalkylene.
Background technology
Epoxides is a kind of important oxygen-containing organic compound.For example, propylene oxide is a kind of important substantially organic
Industrial chemicals, yield is only second to polypropylene in acryloyl derivative.The purposes of propylene oxide maximum is production polyether polyol, with
It is processed further manufacture polyurethane, it can also be used to produce widely used propane diols.In addition, propylene oxide can be additionally used in table
The production of face activating agent, oil field demulsifier etc..
With the extensive use of the materials such as polyurethane, the demand of propylene oxide rises year by year.It is but industrial at present raw
The technique of production propylene oxide still has drawback, can not especially meet the requirement of green chemistry chemical technology.Therefore, there is an urgent need to open
Hair is not only economical but also environment amenable propylene oxide production process.
The appearance of Titanium Sieve Molecular Sieve is that oxidation of alkene epoxidation, phenol hydroxylation, keto-alcohol etc. opens a new way
Footpath, particularly in terms of alkene epoxidation, achieves good catalytic oxidation effect.For example, Dow/BASF and Degussa/
Uhde will using hydrogen peroxide as oxidant, using methanol as solvent, propylene is aoxidized into epoxy processed in the presence of Titanium Sieve Molecular Sieve
The technique of propane is pushed to industrialize.
During using Titanium Sieve Molecular Sieve as catalyst, common problem is, after device operating a period of time, catalyst
Activity and selectivity can reduce, i.e., deactivation phenomenom occurs in catalyst in operation process.At present main settling mode be by
Decaying catalyst carries out in-situ regeneration or ex-situ regeneration so that renewing catalyst activity.Wherein, in-situ regeneration is mainly for catalysis
The lighter situation of agent level of deactivation, generally carries out one using solvent and/or oxidant to decaying catalyst at a certain temperature
The dipping of section time or flushing；Ex-situ regeneration usually urges inactivation mainly for the more serious situation of catalyst inactivation
Agent is roasted.Industrially, it is general using first renewing catalyst activity is made through in-situ regeneration, it can not make to urge in in-situ regeneration
During agent activation recovering, then using ex-situ regeneration.
But when putting into operation again through regenerated catalyst, when particularly putting into operation again after in-situ regeneration, urge
The activity and selectivity fluctuation of agent is larger, it is necessary to be lot more time to stablize；Reaction temperature etc. is improved it is also desirable to combine
Operate to realize the even running of reaction, but can so further speed up catalyst inactivation.
Therefore, the service life of catalyst is extended, particularly the single trip use service life, so as to reduce the regeneration frequency of catalyst
It is still the technical problem of the reaction system urgent need to resolve using Titanium Sieve Molecular Sieve as catalyst.
The content of the invention
It is an object of the invention to provide a kind of method of oxyalkylene, this method can effectively extend as catalyst
Titanium Sieve Molecular Sieve the single trip use service life.
The present invention provides a kind of method of oxyalkylene, this method is included under oxidation reaction condition, makes a kind of liquid
Mixture and Titanium Sieve Molecular Sieve haptoreaction in the reactor, the liquid mixture contain alkene, at least one oxidant with
And optional at least one solvent, wherein, this method further includes the set-up procedure at least carried out once, in the condition 1 of satisfaction into
The row set-up procedure, to improve desirable oxidation selectivity of product until meeting to stop the set-up procedure during condition 2,
Condition 1, sometime the desirable oxidation selectivity of product S under ttWith initial target oxidation product selectivity S0Ratio
Value St/S0For 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0For 0.9≤
S’/S0≤1；
The set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A：Improve the catalytic temperature；
Set-up procedure B：Improve the quality of oxidant in the liquid mixture.
Method oxyalkylene using the present invention, can effectively extend the one way of the Titanium Sieve Molecular Sieve as catalyst makes
With the service life, the regeneration frequency of catalyst is reduced, while production efficiency is improved, it is possible to increase operation stability, extends catalysis
The terminal life of agent.
Method oxyalkylene using the present invention, in continuous operational process for a long time, can select desirable oxidation product
Property stabilization is low to the selectivity of accessory substance in higher level.
Method is simple by the present invention, suitable for large-scale application.
Embodiment
The present invention provides a kind of method of oxyalkylene, this method is included under oxidation reaction condition, makes a kind of liquid
Mixture and Titanium Sieve Molecular Sieve haptoreaction in the reactor, the liquid mixture contain alkene, at least one oxidant with
And optional at least one solvent.
In the present invention, " at least one " represents one or more (such as two or more)；It is " optional " represent with or without.
The method according to the invention, the oxidant can be it is common it is various can be by the material of olefin oxidation.It is preferred that
Ground, the oxidant are peroxide.The peroxide refers to the compound for containing-O-O- keys in molecular structure, Ke Yixuan
From hydrogen peroxide, organic peroxide and peracid.The organic peroxide refers to one or two in hydrogen peroxide molecule
Material obtained from hydrogen atom is substituted by organic group.The peracid refers to the organic oxygen-containing for containing-O-O- keys in molecular structure
Acid.The instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, tert-butyl hydroperoxide, peroxidating isopropyl
Benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, so can be into one
Step reduces separation costs.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.
The dosage of the oxidant can make choice according to the amount of alkene.Usually, the alkene and the oxidant
Molar ratio can be in 0.1-10：In the range of 1, preferably in 0.2-5：In the range of 1, more preferably in 0.5-3：In the range of 1,
Further preferably in 1-2：In the range of 1.
The method according to the invention, the liquid mixture can contain solvent, can not also contain solvent, preferably also contain
There is at least one solvent, can so better control over the speed and severe degree of reaction.Kind of the present invention for the solvent
Class is not particularly limited, and the solvent can be common various solvents in olefin hydrocarbon oxidation reaction.Preferably, the solvent is
Water, C1-C10Alcohol, C3-C10Ketone, C2-C10Nitrile and C1-C6At least one of carboxylic acid.Preferably, the solvent is C1-
C6Alcohol, C3-C8Ketone and C2-C5One or both of nitrile more than.It is highly preferred that the solvent is methanol, ethanol, positive third
It is more than one or both of alcohol, isopropanol, the tert-butyl alcohol, isobutanol and acetone.It is further preferred that the solvent for methanol,
It is more than one or both of acetone and the tert-butyl alcohol.
The present invention is not particularly limited for the dosage of the solvent, can be selected according to the amount of alkene and oxidant
Select.Usually, the molar ratio of the solvent and the alkene can be 1-100：1, it is preferably 2-80：1, more preferably 3-40：
1, more preferably 4-10：1.
The method according to the invention, according to specific needs, the liquid mixture can also contain at least one basic species
Matter, the pH value of the liquid mixture is adjusted within the scope of being in 6.5-9, can so be further improved for ring
The selectivity of oxide.The instantiation of the alkaline matter can include but is not limited to：Ammonia (that is, NH3), amine, quaternary ammonium base and M1
(OH)n(wherein, M1For alkali or alkaline earth metal, such as sodium, potassium, magnesium or calcium；N is and M1The identical integer of chemical valence).
The method of the present invention can be used for aoxidizing a variety of alkene.The alkene can be C2-C16Alkene.It is described
Alkene can be monoolefine, or polyene, is preferably monoolefine.Specifically, the alkene is propylene and/or butylene.
The method according to the invention, Titanium Sieve Molecular Sieve are a kind of boilings of a part of silicon atom in titanium atom substitution lattice framework
The general name of stone, can use chemical formula xTiO2·SiO2Represent.Content no spy of the present invention for titanium atom in Titanium Sieve Molecular Sieve
Do not limit, can be the conventional selection of this area.Specifically, x can be 0.0001-0.05, be preferably 0.01-0.03, more excellent
Elect 0.015-0.025 as.
The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as：The titanium silicon
Molecular sieve can be selected from Titanium Sieve Molecular Sieve (such as TS-1), Titanium Sieve Molecular Sieve (such as TS-2), the BEA structures of MEL structures of MFI structure
Titanium Sieve Molecular Sieve (such as Ti-Beta), Titanium Sieve Molecular Sieve (such as Ti-MCM-22), the Titanium Sieve Molecular Sieve of MOR structures of MWW structures
Titanium Sieve Molecular Sieve (such as Ti-MCM- of the Titanium Sieve Molecular Sieve (such as Ti-TUN) of (such as Ti-MOR), TUN structures, two-dimentional hexagonal structure
41st, Ti-SBA-15) and other structures Titanium Sieve Molecular Sieve (such as Ti-ZSM-48).The Titanium Sieve Molecular Sieve is preferably selected from MFI
The Titanium Sieve Molecular Sieve of structure, the Titanium Sieve Molecular Sieve of MEL structures, the two-dimentional Titanium Sieve Molecular Sieve of hexagonal structure and the titanium silicon of BEA structures
The Titanium Sieve Molecular Sieve of molecular sieve, more preferably MFI structure.
Preferably, the Titanium Sieve Molecular Sieve is hollow Titanium Sieve Molecular Sieve, can so obtain further extended catalyst
The single trip use service life, while more preferable catalytic effect can also be obtained.The hollow Titanium Sieve Molecular Sieve is the titanium silicon molecule of MFI structure
Sieve, the crystal grain of the Titanium Sieve Molecular Sieve is hollow-core construction, and the radical length of the chamber portion of the hollow-core construction is 5-300 nanometers, and
The Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, the benzene adsorbance measured under conditions of when adsorption time is 1 small is at least 70 millis
Gram gram, there are hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve.It is described hollow
Titanium Sieve Molecular Sieve be commercially available (such as commercially available from Hunan Jianchang Petrochemical Co., Ltd the trade mark be HTS molecule
Sieve), it can also be prepared according to the method disclosed in CN1132699C.
The method according to the invention, the Titanium Sieve Molecular Sieve and the contact form of the liquid mixture do not limit especially
It is fixed, Titanium Sieve Molecular Sieve can be seated in the catalyst bed of fixed bed reactors, pass through the liquid mixture described
Catalyst bed, so as to fulfill in the presence of Titanium Sieve Molecular Sieve, by alkene and oxidant haptoreaction；Can also be by the liquid
Mixture is mixed to form slurry with Titanium Sieve Molecular Sieve, and so as to fulfill in the presence of Titanium Sieve Molecular Sieve, alkene is contacted with oxidant
Reaction.
It can be used when the liquid mixture and Titanium Sieve Molecular Sieve are mixed to form slurry, after the completion of haptoreaction each
Slurry is carried out solid-liquor separation by kind method, so as to obtain the liquid material containing desirable oxidation product.Such as：Film point can be passed through
The liquid material is subjected to solid-liquor separation from device.
When the Titanium Sieve Molecular Sieve is seated in the catalyst bed of fixed bed reactors, the catalyst bed
Quantity can be one or more.When the quantity of catalyst bed is multiple, the different zones of a reactor can be located at,
It can also be located in multiple reactors.
In one embodiment of the invention, the catalyst bed contains the first catalyst bed and the second catalyst
Bed, on the basis of the flow direction of the liquid mixture, first catalyst bed is located at second catalyst bed
The upstream of layer, i.e., described liquid mixture firstly flow through the first catalyst bed, again pass through the second catalyst bed.Described first urges
Agent bed can be identical with the species for the Titanium Sieve Molecular Sieve loaded in second catalyst bed, or different.
Preferably, the Titanium Sieve Molecular Sieve of first catalyst bed filling is hollow Titanium Sieve Molecular Sieve, second catalyst bed
The Titanium Sieve Molecular Sieve of filling is the Titanium Sieve Molecular Sieve (example of the Titanium Sieve Molecular Sieve in addition to hollow Titanium Sieve Molecular Sieve, such as other MFI structures
Such as titanium-silicon molecular sieve TS-1), the Titanium Sieve Molecular Sieve (such as Titanium Sieve Molecular Sieve Ti-MCM-41) and BEA structures of two-dimentional hexagonal structure
One or both of Titanium Sieve Molecular Sieve (such as Titanium Sieve Molecular Sieve Ti-Beta) more than, so can further delay titanium silicon
The deactivation rate of molecular sieve.It is highly preferred that the Titanium Sieve Molecular Sieve of the first catalyst bed filling is hollow Titanium Sieve Molecular Sieve,
The Titanium Sieve Molecular Sieve of the second catalyst bed filling is titanium-silicon molecular sieve TS-1, so can not only further extend titanium silicon
The single trip use service life of molecular sieve, and selectivity of product can also be further improved.
When the catalyst bed contains the first catalyst bed and the second catalyst bed, first catalyst bed
The weight ratio of Titanium Sieve Molecular Sieve of the Titanium Sieve Molecular Sieve loaded in layer with being loaded in second catalyst bed can be 0.1-
20：1.The Titanium Sieve Molecular Sieve loaded in first catalyst bed and the titanium silicon molecule loaded in second catalyst bed
The weight ratio of sieve is preferably more than 0.5, more preferably more than 1, more preferably more than 2.In first catalyst bed
The weight ratio of Titanium Sieve Molecular Sieve of the Titanium Sieve Molecular Sieve of filling with being loaded in second catalyst bed is preferably less than 15, more
Preferably less than 10.It is further preferred that the Titanium Sieve Molecular Sieve loaded in first catalyst bed is urged with described second
The weight ratio for the Titanium Sieve Molecular Sieve loaded in agent bed is 2-10：1.
When the catalyst bed contains the first catalyst bed and the second catalyst bed, the liquid mixture stream
The superficial velocity for crossing the first catalyst bed and the second catalyst bed can be identical, or different.Preferably, it is described
The superficial velocity that liquid mixture flows through the first catalyst bed is v1, the superficial velocity for flowing through the second catalyst bed is v2, its
In, v1＜ v2, so can further extend the single trip use service life of Titanium Sieve Molecular Sieve, while the oxidant of higher can also be obtained
Effective rate of utilization and desirable oxidation selectivity of product.It is highly preferred that v2/v1=1.5-15.v2/v1Preferably more than 2.v2/v1It is excellent
Elect less than 10 as, more preferably less than 5.It is further preferred that v2/v1=2-5.
In the present invention, the superficial velocity (flow velocity) refers to mix by the liquid of catalyst bed whole process in the unit interval
The area of the mass flow (in terms of kg/s) of thing and a certain cross section of catalyst bed is (with m2Meter) ratio.Can be by unit
The quality of the liquid mixture of fixed bed reactors is sent into time as " by the liquid of whole catalyst beds in the unit interval
The mass flow of body mixture ".In the present invention, for superficial velocity of the liquid mixture in the first catalyst bed without spy
It is different to require, generally can be in 0.001-200kg/ (m2S) in the range of.
The liquid mixture can be adjusted using various methods in the first catalyst bed and the second catalyst bed
In superficial velocity.For example, the superficial velocity of liquid mixture can be adjusted by the cross-sectional area of selecting catalyst bed.
Specifically, the cross-sectional area of first catalyst bed can be made to be more than the cross-sectional area of second catalyst bed, from
And cause v1＜ v2.Specifically, the internal diameter of first catalyst bed is D1, the internal diameter of second catalyst bed is D2,
Wherein, D1＞ D2。D1/D2Preferably more than 1.5, more preferably more than 2.D1/D2Preferably less than 15, more preferably less than 10,
More preferably less than 5.Specifically, D1/D2It can be 1.5-15, be preferably 2-5.
The method according to the invention, contains the first catalyst bed and the second catalyst bed in the catalyst bed
When, residence time of the liquid mixture in the first catalyst bed is T1, the total residence time in catalyst bed
For T, it is preferable that T1/ T=0.2-0.95, can so obtain the further extended catalyst single trip use service life, while can also
Obtain more preferable reaction effect.T1/ T is preferably more than 0.3, and more preferably more than 0.5.T1/ T is preferably less than 0.9, more preferably
For less than 0.85.It is further preferred that T1/ T=0.5-0.85.
The method according to the invention, as the case may be can be between the first catalyst bed and the second catalyst bed
Fresh material is supplemented, when the first catalyst bed and/or the second catalyst bed are multiple catalyst beds, according to specific feelings
Condition can supplement delivered fresh between the first catalyst bed and/or between the second catalyst bed into the liquid mixture
Material.Such as：Between the first catalyst bed and the second catalyst bed, between the first catalyst bed and/or second catalysis
Supplemented more than one or both of alkene, oxidant and optional solvent between agent bed.However, it is desirable to explanation, institute
State whole beds (that is, the whole process of the first catalyst bed) and the second catalyst that liquid mixture flows through the first catalyst bed
Whole beds (that is, the whole process of the second catalyst bed) of bed, the liquid mixture is not included in the first catalyst bed
The delivered fresh introduced between layer, between the second catalyst bed and between the first catalyst bed and the second catalyst bed
Material, previously described superficial velocity determines by the liquid mixture, from whether the influence of fresh material is introduced.
When the catalyst bed contains the first catalyst bed and the second catalyst bed, first catalyst bed
Layer and the second catalyst bed can each contain one or more catalyst beds.In the first catalyst bed and/or second
Can be to be connected in series when catalyst bed contains multiple catalyst beds, between multiple catalyst beds, or in parallel
Connection, can also be series connection and combination in parallel, such as：Multiple catalyst beds are divided into multigroup, the catalyst bed in every group
Layer is to be connected in series and/or be connected in parallel to be connected in series and/or being connected in parallel, between each group.First catalyst bed
The different zones of same reactor can be arranged on second catalyst bed, different reactors can also be arranged on
In.
The method according to the invention, the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or shaping titanium silicon
Molecular sieve, is preferably molded Titanium Sieve Molecular Sieve.Shaping Titanium Sieve Molecular Sieve typically contain Titanium Sieve Molecular Sieve as active component and
As the carrier of binding agent, wherein, the content of Titanium Sieve Molecular Sieve can be conventional selection.Usually, with the shaping titanium silicon point
On the basis of the total amount of son sieve, the content of Titanium Sieve Molecular Sieve can be 5-95 weight %, be preferably 10-95 weight %, more preferably
70-90 weight %；The content of the carrier can be 5-95 weight %, be preferably 5-90 weight %, more preferably 10-30 weights
Measure %.The carrier of the shaping Titanium Sieve Molecular Sieve can be conventional selection, such as aluminium oxide and/or silica.Prepare the shaping
The method of Titanium Sieve Molecular Sieve is it is known in the art, being no longer described in detail herein.The granular size of the shaping Titanium Sieve Molecular Sieve
It is not particularly limited, can be made appropriate choice according to concrete shape.Usually, the average grain of the shaping Titanium Sieve Molecular Sieve
Footpath can be 4-5000 microns, be preferably 5-2000 microns, such as 40-1000 microns.The average grain diameter is volume average particle size,
Laser particle analyzer can be used to measure.
The dosage of the Titanium Sieve Molecular Sieve can make choice according to the specific treating capacity of device.Usually, the alkene
Weight (hourly) space velocity (WHSV) can be 0.1-20h-1, it is preferably 1-10h-1.The weight (hourly) space velocity (WHSV) is on the basis of the total amount of Titanium Sieve Molecular Sieve.
The method according to the invention, catalyst bed can only load Titanium Sieve Molecular Sieve, can also contain Titanium Sieve Molecular Sieve
And inactive filler.Inactive filler is loaded in catalyst bed to carry out the amount of Titanium Sieve Molecular Sieve in catalyst bed
Adjustment, so that the speed of reaction be adjusted.When the catalyst bed contains Titanium Sieve Molecular Sieve and inactive filler, urge
The content of inactive filler can be 5-95 weight % in agent bed.The inactive filler refer to oxidation reaction without or
The basic filler without catalytic activity, its instantiation can include but is not limited to：In quartz sand, ceramic ring and potsherd
It is one or more.
The method according to the invention, further includes the set-up procedure at least carried out once, the tune is carried out in the condition 1 of satisfaction
Synchronizing is rapid, to improve desirable oxidation selectivity of product until meeting to stop the set-up procedure during condition 2,
Condition 1, sometime the desirable oxidation selectivity of product S under ttWith initial target oxidation product selectivity S0Ratio
Value St/S0For 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0For 0.9≤
S’/S0≤1；
The set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A：The catalytic temperature is improved (that is, when liquid mixture is with Titanium Sieve Molecular Sieve haptoreaction
Temperature)；
Set-up procedure B：Improve the quality of oxidant in the liquid mixture.
The method according to the invention, in the condition 2 of satisfaction, stops improving catalytic temperature and by catalytic temperature
Degree remains the temperature after rise；When the method for the present invention further includes set-up procedure B, in the condition 2 of satisfaction, stop improving liquid
The quality of oxidant and the numerical value when quality of oxidant to be remained to the condition 2 of satisfaction in body mixture.
The set-up procedure is carried out when meeting above-mentioned condition 1, the desirable oxidation production that downward trend is presented originally can be made
Thing selectively gos up, and desirable oxidation selectivity of product is promoted to higher level, so as to extend the single trip use of Titanium Sieve Molecular Sieve
Service life, and desirable oxidation selectivity of product is maintained into higher level for a long time.
On the premise of it can extend the single trip use service life of Titanium Sieve Molecular Sieve, from during further extension device stable operation
Between angle set out, in condition 1, St/S0<0.9。
In the present invention, desirable oxidation selectivity of product=(molal quantity of desirable oxidation product in obtained reaction mixture/
Participate in the molal quantity of the alkene of reaction) × 100%；
Wherein, the molal quantity=molal quantity of the alkene of addition-of the alkene of reaction is participated in obtained reaction mixture
The molal quantity of alkene.
The composition of the reaction mixture that can be exported by continuous monitoring during the reaction from reactor determines mesh
Mark oxidation product selectivity S0、StAnd S '.When reactor is multiple reactors, on the basis of the flow direction of liquid mixture,
Desirable oxidation selectivity of product S is determined by the reaction mixture of the reactor output positioned at logistics end0、StAnd S '.
In the present invention, initial target oxidation product selectivity S0After reactor stable operation, from the head of reactor output
The composition of batch reaction mixture determines.For example, can by reactor stable operation 0.5-10 when small within obtained reaction mix
Thing is as first batch of reaction mixture.
Conventional method can be used to measure the composition of the reaction mixture exported from reactor, such as gas chromatography.
Although in the condition 1 of satisfaction, improve catalytic temperature and alternatively improve oxidant in liquid mixture
Quality until meet condition 2, but in set-up procedure A, haptoreaction is preferably improved with 0.01-2 DEG C/day of amplitude
Temperature；In set-up procedure B, the quality of oxidant in liquid mixture is preferably improved with the amplitude in 0.02-5%/day, so
The longer Titanium Sieve Molecular Sieve single trip use service life can be obtained, moreover it is possible to reaction is more smoothly carried out.In the present invention, " amplitude "
Refer to the step-length between two neighboring numerical value.
The method according to the invention, the raising degree of catalytic temperature cause catalytic temperature to be preferably no greater than
120℃.The catalytic initial temperature is generally more than 0 DEG C.From the selectivity further improved for epoxides
Angle is set out, and the catalytic initial temperature is preferably in the range of 20-80 DEG C, more preferably in the range of 30-60 DEG C,
In the range of more preferably 30-50 DEG C.
The liquid mixture and the catalytic temperature of Titanium Sieve Molecular Sieve can be improved using common various methods,
Such as：The amount for the reaction heat that the heating-up temperature of raising catalyst bed, reduction are taken out by heat transferring medium from catalyst bed,
Improve the feeding temperature of liquid mixture or the combination of both or three in above-mentioned three.
Method according to the invention it is possible to the quality of oxidant in liquid mixture is improved using various methods.Such as：
The additive amount that oxidant when preparing the liquid mixture can be improved improves the quality of oxidant in liquid mixture.In oxygen
When agent provides in the form of a solution, liquid can also be improved by way of the concentration of oxidant in oxidizing agent solution and mixed improving
The quality of oxidant in compound, at this time the dosage of oxidizing agent solution can remain unchanged that (at this time, the research on maximum utilized quantity of oxidant causes
The molar ratio of oxidant and alkene is preferably no greater than 10：1, more preferably no higher than 5：1, further preferably not higher than 3：1), also may be used
To be accordingly adjusted (for example, the dosage of oxidizing agent solution is accordingly reduced, to keep the ratio between alkene and oxidant not
Become), as long as the quality that can ensure that oxidant in liquid mixture is raising., can will at least portion in actual mechanical process
Divide solvent to be mixed with oxidant, so as to prepare oxidizing agent solution, the concentration of oxidant in oxidizing agent solution is gradually stepped up, to improve
The quality of oxidant in liquid mixture, while realizing makes reaction carry out in the presence of at least one solvent.
The method according to the invention, in continuous operational process for a long time, the increase rate of haptoreaction temperature and can
The increase rate of the oxidant quality of choosing can be identical or different.Usually, in the reaction early period can relatively low amplitude carry
High haptoreaction temperature and optional oxidant quality, the phase can be with higher amplitude raising haptoreaction temperature after the reaction
And optional oxidant quality.
The method according to the invention, when being adjusted step, remaining condition generally remains unchanged, naturally it is also possible to phase
It should be adjusted.
The method according to the invention, the set-up procedure are set-up procedure A or the group of set-up procedure A and set-up procedure B
Close.
Set-up procedure A can be used alone, i.e. in the condition 1 of satisfaction, can only be adjusted step A.
Set-up procedure A can also be applied in combination with set-up procedure B.
When set-up procedure A and set-up procedure B are applied in combination, in the first embodiment, in the condition 1 of satisfaction,
Be adjusted step A and set-up procedure B, set-up procedure A and set-up procedure B can be carried out synchronously at this time, can also it is asynchronous into
OK, preferably asynchronous progress, is so more advantageous to operating, while is also easier to be controlled reaction.
When set-up procedure A and set-up procedure B are applied in combination, in second of embodiment, in the condition 1 of satisfaction,
Step A or set-up procedure B is adjusted, wherein, set-up procedure A at least once is carried out between the adjacent B of set-up procedure twice,
Such as 1-5 (preferably 1-3 times) set-up procedure A.That is, condition 1 is met common n times, wherein, n1It is secondary when meeting condition 1, it is adjusted step
Rapid A, n2It is secondary when meeting condition 1, it is adjusted step B, n1+n2=n, n1≥n2, such as n1/n2=1-5, preferably n1/n2=1-3.
When set-up procedure A and set-up procedure B are applied in combination, in the third embodiment, in the condition 1 of satisfaction,
Step A or set-up procedure B is adjusted, wherein, set-up procedure B at least once is carried out between the adjacent A of set-up procedure twice,
Such as 1-5 (preferably 1-3 times) set-up procedure B.That is, common n ' is secondary to meet condition 1, wherein, n1' secondary when meeting condition 1, it is adjusted
Step B, n2' secondary when meeting condition 1, it is adjusted step A, n1’+n2'=n ', n1’≥n2', such as n1’/n2'=1-5, preferably
n1’/n2'=1-3.
Preferably, set-up procedure A and set-up procedure B are applied in combination, so can more effectively extend the list of catalyst
Journey service life, obtains the desirable oxidation selectivity of product of higher.
The method according to the invention, remaining condition of oxidation reaction can be conventional selection.Usually, in terms of gauge pressure, instead
It can be 0-5MPa to answer the pressure in device, be preferably 0.1-3MPa.
The method according to the invention can also include being separated the reaction mixture exported from reactor, to obtain
Desirable oxidation product (such as epoxides) and unreacted reactant.It can be this that reaction mixture is carried out separated method
The conventional selection in field, is not particularly limited.The unreacted reactant isolated can recycle.
The method according to the invention, can effectively extend the single trip use service life of the Titanium Sieve Molecular Sieve as catalyst, make
Device can the stable operation in longer time, reduce operating cost；Also, the method for the present invention is for by olefin oxidation system
During standby epoxides, higher epoxide selectivities can be obtained.
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, if not otherwise specified, agents useful for same is commercially available analytical reagents, and pressure is equal
For gauge pressure, Titanium Sieve Molecular Sieve used is fresh Titanium Sieve Molecular Sieve.
Hollow Titanium Sieve Molecular Sieve used is according to public in Chinese patent CN1132699C in following embodiments and comparative example
Prepared by the method opened, its titanium oxide content is 2.5 weight %；Titanium-silicon molecular sieve TS-1 used is by Journal of
Natural Gas Chemistry,2001,10(4):In 295-307 prepared by the described method of the 9-24 rows of page 296,
Its titanium oxide content is 2.5 weight %；Ti-MCM-41 Titanium Sieve Molecular Sieve used be according to Corma etc. in Chem.Commun.,
Prepared by the method described in 1994,147-148, its titanium oxide content is 3 weight %；Ti-Beta titanium silicon molecules used
Sieve for according to Takashi Tatsumi etc. in J.Chem.Soc.Chem.Commun., the method described in 1997,677-678
Prepare, its titanium oxide content is 2.6 weight %.
In following embodiments and comparative example, using gas chromatography come the content of each component in the reaction solution analyzed,
The following formula is respectively adopted on this basis to calculate oxidant effective rate of utilization, the epoxides choosing as desirable oxidation product
Selecting property and the acetaldehyde selectivity as accessory substance：
Oxidant effective rate of utilization=(mole of the oxidant of the molal quantity of the epoxides of reaction generation/reaction consumption
Number) × 100%；
Epoxide selectivities=(molal quantity of the alkene of the molal quantity of the epoxides of reaction generation/reaction consumption) ×
100%；
Acetaldehyde selectivity=(molal quantity of the alkene of the molal quantity of the acetaldehyde of reaction generation/reaction consumption) × 1000000.
Embodiment 1-20 is used for the method for illustrating the present invention.
Embodiment 1
By catalyst, (volume average particle size is 700 μm of spheric catalyst, the content of titanium-silicon molecular sieve TS-1 in catalyst
For 80 weight %, the content of silica is 20 weight %, density 0.74g/cm3) be seated in fixed bed reactors, formed etc.
Footpath catalyst bed, wherein, the quantity of catalyst bed is 1 layer.
Using propylene, the hydrogen peroxide (offer in the form of the hydrogen peroxide of 30 weight %) as oxidant and it is used as solvent
It is sent into after acetone mixing from the bottom of fixed bed reactors and flows through catalyst bed.Wherein, mole of propylene and hydrogen peroxide
Than for 1：0.5, the molar ratio of propylene and solvent acetone is 1：5, the weight (hourly) space velocity (WHSV) of propylene is 1.5h-1.Initial reaction temperature is 40
DEG C, it is 2.0MPa to control the pressure in fixed bed reactors in reaction process.
The composition for the reaction mixture that continuous monitoring is exported from reactor in reaction process, in propylene oxide selectivity St
With initial (reaction is measured by sampling when proceeding to 0.5 hour) propylene oxide selectivity S0Ratio St/S0For 0.85≤St/S0<0.9
When (that is, when meeting condition 1), reaction temperature is improved with 0.02-2 DEG C/day of amplitude until propylene oxide selectivity S ' with it is initial
Propylene oxide selectivity S0Ratio S '/S0For 0.9≤S '/S0When≤1 (that is, when meeting condition 2), stop improving reaction temperature
And remain at the temperature after rise.
Carry out 800 it is small when reaction, at the end of reaction reaction temperature be 72 DEG C.React 0.5 it is small when and 800 it is small when obtain
Oxidant effective rate of utilization, propylene oxide selectivity and acetaldehyde are selectively listed in table 1.
Embodiment 2
Using method propylene oxide same as Example 1, the difference is that, in reaction process, meet condition 1 at the 1st time
When, reaction temperature is improved with 0.02-2 DEG C/day of amplitude until when meeting condition 2, stops improving reaction temperature and is kept
For the temperature after rise；When meeting condition 1 the 2nd time, hydrogen peroxide in liquid mixture is improved with the amplitude in 0.02-5%/day
Quality (realized by the concentration for improving hydrogen peroxide in hydrogen peroxide, the corresponding dosage for reducing hydrogen peroxide, to keep hydrogen peroxide
It is constant with the molar ratio of propylene) until when meeting condition 2, stop improving the quality of hydrogen peroxide in liquid mixture and remain
Numerical value after rise, and so on (that is, when odd-times meets condition 1, reaction temperature is improved with 0.02-2 DEG C/day of amplitude
Degree is until meet condition 2；When even-times meets condition 1, peroxide in liquid mixture is improved with the amplitude in 0.02-5%/day
Change the quality of hydrogen until meeting condition 2).
Carry out 850 it is small when reaction, at the end of reaction reaction temperature be 55 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 60
Weight %.React 0.5 it is small when and 850 it is small when obtained result listed in table 1.
Comparative example 1
Using method propylene oxide same as Example 1, unlike, do not change the temperature of reaction in reaction process.
React 0.5 it is small when and 360 it is small when result listed in table 1.
Embodiment 3
Using method propylene oxide same as Example 2, the difference is that, the titanium-silicon molecular sieve TS-1 in catalyst is used etc.
Amount hollow Titanium Sieve Molecular Sieve replace (that is, be molded hollow Titanium Sieve Molecular Sieve, the content of hollow Titanium Sieve Molecular Sieve is 80 weight %,
The content of silica is 20 weight %, and the density of catalyst is 0.69g/cm3)。
Carry out 880 it is small when reaction, at the end of reaction reaction temperature be 48 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 57
Weight %.React 0.5 it is small when and 880 it is small when result listed in table 1.
Embodiment 4
Using method propylene oxide same as Example 2, the difference is that, the titanium-silicon molecular sieve TS-1 in catalyst is used etc.
The Titanium Sieve Molecular Sieve Ti-MCM-41 of amount replace (that is, be molded Titanium Sieve Molecular Sieve Ti-MCM-41, Titanium Sieve Molecular Sieve Ti-MCM-41's
Content is 80 weight %, and the content of silica is 20 weight %, and the density of catalyst is 0.62g/cm3)。
Carry out 800 it is small when reaction, at the end of reaction reaction temperature be 53 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 63
Weight %.React 0.5 it is small when and 800 it is small when result listed in table 1.
Embodiment 5
Using method propylene oxide same as Example 2, the difference is that, the titanium-silicon molecular sieve TS-1 in catalyst is used etc.
The Titanium Sieve Molecular Sieve Ti-Beta of amount replaces (that is, being molded Titanium Sieve Molecular Sieve Ti-Beta, the content of Titanium Sieve Molecular Sieve Ti-Beta is
80 weight %, the content of silica is 20 weight %, and the density of catalyst is 0.77g/cm3)。
Carry out 820 it is small when reaction, at the end of reaction reaction temperature be 54 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 61
Weight %.React 0.5 it is small when and 820 it is small when result listed in table 1.
Embodiment 6
Using method propylene oxide same as Example 2, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, first filling shaping hollow titanium si molecular sieves (same as Example 3), reloading is molded titanium-silicon molecular sieve TS-1
(same as Example 1), so as to form catalyst bed, i.e., liquid mixture is first passed through is formed by being molded hollow Titanium Sieve Molecular Sieve
Catalyst bed, then the catalyst bed by being formed by shaping titanium-silicon molecular sieve TS-1.Wherein, it is molded hollow titanium silicon molecule
The weight ratio of sieve and shaping titanium-silicon molecular sieve TS-1 is 2：1.
Carry out 1200 it is small when reaction, at the end of reaction reaction temperature be 51 DEG C, the concentration of hydrogen peroxide is in hydrogen peroxide
56 weight %.React 0.5 it is small when and 1200 it is small when result listed in table 1.
Embodiment 7
Using method propylene oxide same as Example 6, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, first filling shaping titanium-silicon molecular sieve TS-1, reloading is molded hollow Titanium Sieve Molecular Sieve, and (that is, liquid mixture is first
By being molded titanium-silicon molecular sieve TS-1, then by being molded hollow Titanium Sieve Molecular Sieve) so that catalyst bed is formed, wherein, shaping
Titanium-silicon molecular sieve TS-1 is 1 with the weight ratio for being molded hollow Titanium Sieve Molecular Sieve：2.
Carry out 830 it is small when reaction, at the end of reaction reaction temperature be 56 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 57
Weight %.React 0.5 it is small when and 830 it is small when result listed in table 1.
Embodiment 8
Using method propylene oxide same as Example 6, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, it is 1 to be molded hollow Titanium Sieve Molecular Sieve with the weight ratio for being molded titanium-silicon molecular sieve TS-1：1.
Carry out 1000 it is small when reaction, at the end of reaction reaction temperature be 55 DEG C, the concentration of hydrogen peroxide is in hydrogen peroxide
56 weight %.React 0.5 it is small when and 1000 it is small when result listed in table 1.
Embodiment 9
Using method propylene oxide same as Example 6, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, it is 1 to be molded hollow Titanium Sieve Molecular Sieve with the weight ratio for being molded titanium-silicon molecular sieve TS-1：2.
Carry out 960 it is small when reaction, at the end of reaction reaction temperature be 57 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 58
Weight %.React 0.5 it is small when and 960 it is small when result listed in table 1.
Embodiment 10
Using method propylene oxide same as Example 6, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, it is 8 to be molded hollow Titanium Sieve Molecular Sieve with the weight ratio for being molded titanium-silicon molecular sieve TS-1：1.
Carry out 1200 it is small when reaction, at the end of reaction reaction temperature be 53 DEG C, the concentration of hydrogen peroxide is in hydrogen peroxide
55 weight %.React 0.5 it is small when and 1200 it is small when result listed in table 1.
Embodiment 11
Using method propylene oxide same as Example 6, the difference is that, it is being molded the total filling amount of Titanium Sieve Molecular Sieve not
Under conditions of change, it is 20 to be molded hollow Titanium Sieve Molecular Sieve with the weight ratio for being molded titanium-silicon molecular sieve TS-1：1.
Carry out 1050 it is small when reaction, at the end of reaction reaction temperature be 55 DEG C, the concentration of hydrogen peroxide is in hydrogen peroxide
53 weight %.React 0.5 it is small when and 1050 it is small when result listed in table 1.
Embodiment 12
Using method propylene oxide same as in Example 10, the difference is that, shaping titanium-silicon molecular sieve TS-1 equivalent
It is molded Titanium Sieve Molecular Sieve Ti-MCM-41 replacements (same as Example 4).
Carry out 980 it is small when reaction, at the end of reaction reaction temperature be 57 DEG C, in hydrogen peroxide the concentration of hydrogen peroxide be 59
Weight %.React 0.5 it is small when and 980 it is small when result listed in table 1.
Embodiment 13
Using method propylene oxide same as in Example 10, the difference is that, shaping titanium-silicon molecular sieve TS-1 equivalent
It is molded Titanium Sieve Molecular Sieve Ti-Beta replacements (same as Example 5).
Carry out 1000 it is small when reaction, at the end of reaction reaction temperature be 56 DEG C, the concentration of hydrogen peroxide is in hydrogen peroxide
57 weight %.React 0.5 it is small when and 1000 it is small when result listed in table 1.
Table 1
By embodiment 1 as can be seen that method using the present invention can be using as catalyst compared with comparative example 1
The catalytic activity of Titanium Sieve Molecular Sieve maintains higher level for a long time, so as to effectively extend the single trip use longevity of Titanium Sieve Molecular Sieve
Life, while remain able to obtain higher oxidant effective rate of utilization.
By embodiment 1 as can be seen that reaction temperature will be improved and improve oxygen in liquid mixture compared with embodiment 2
The mass combination of agent uses, and can further extend the single trip use service life of Titanium Sieve Molecular Sieve.
Embodiment 14
(volume average particle size is filling shaping hollow titanium si molecular sieves respectively in the fixed bed reactors of two series connection
200 μm of spheric catalyst, density 0.71g/cm3, wherein, the content of hollow Titanium Sieve Molecular Sieve is 85 weight %, silica
Content be 15 weight %), formed catalyst bed, wherein, the quantity of each catalyst reactor bed is 1 layer.With
On the basis of the flow direction of liquid material in the reactor, the catalyst bed in the fixed bed reactors of upstream is known as
First catalyst bed, is known as the second catalyst bed by the catalyst bed in the fixed bed reactors in downstream, and first
The hollow Titanium Sieve Molecular Sieve of shaping loaded in catalyst bed and the shaping hollow titanium silicon molecule loaded in the second catalyst bed
The weight ratio of sieve is 5：1, the ratio of the internal diameter of the internal diameter of the first catalyst bed and the second catalyst bed is 3：1.
By propylene, hydrogen peroxide (in the form of the hydrogen peroxide of 40 weight % provide) as after the methanol mixing of solvent from positioned at
The bottom of the fixed bed reactors of upstream is sent into and flows through the first catalyst bed, and the liquid mixture of output subsequently enters next
In a fixed bed reactors and flow through the second catalyst bed.Wherein, the molar ratio of propylene and hydrogen peroxide is 3：1, propylene with
The molar ratio of methanol is 1：4, the weight (hourly) space velocity (WHSV) of propylene is 3h-1.Initial reaction temperature in two fixed bed reactors is 30
DEG C, it is 0.2MPa to control the pressure in two fixed bed reactors in reaction process.
The composition for the reaction mixture that continuous monitoring is exported from reactor in reaction process, in propylene oxide selectivity St
With initial (reaction is measured by sampling when proceeding to 2 hours) propylene oxide selectivity S0Ratio St/S0For 0.85≤St/S0<When 0.9
(that is, when meeting condition 1), improving reaction temperature with 0.02-2 DEG C/day of amplitude, (reaction temperature of two reactors remains phase
Together) until propylene oxide selectivity S ' and initial epoxy propane selectivity S0Ratio S '/S0For 0.9≤S '/S0When≤1 (i.e.,
During the condition 2 of satisfaction), stop improving reaction temperature and remain at the temperature after rise.
Carry out 1000 it is small when reaction, at the end of reaction reaction temperature be 72 DEG C.React 2 it is small when and 1000 it is small when obtain
Oxidant effective rate of utilization, propylene oxide selectivity and acetaldehyde are selectively listed in table 2.
Embodiment 15
Using the method propylene oxide identical with embodiment 14, the difference is that, in reaction process, in the 1st and the 2nd satisfaction
During condition 1, reaction temperature (reaction temperature of two reactors remains identical) is improved with 0.02-2 DEG C/day of amplitude until full
During sufficient condition 2, stop improving reaction temperature and remain at the temperature (that is, set-up procedure A) after rise；In the 3rd satisfaction
During condition 1, the quality of hydrogen peroxide in liquid mixture is improved (by improving mistake in hydrogen peroxide with the amplitude in 0.02-5%/day
The concentration of hydrogen oxide realizes that dioxygen water consumption remains unchanged) until when meeting condition 2, stop improving peroxide in liquid mixture
Change the quality of hydrogen and remain the numerical value (that is, set-up procedure B) after rise, and so on (that is, between set-up procedure B twice
Carry out set-up procedure A twice).
Carry out 1200 it is small when reaction, at the end of reaction reaction temperature be 62 DEG C, the concentration of hydrogen peroxide is 50 weight %.Instead
Answer 2 it is small when and 1200 it is small when obtained oxidant effective rate of utilization, propylene oxide selectivity and acetaldehyde selectively arranged in table 2
Go out.
Comparative example 2
Using the method propylene oxide identical with embodiment 14, the difference is that, do not change reaction temperature in reaction process.Instead
Answer 2 it is small when and 400 it is small when result listed in table 2.
Embodiment 16
Using the method propylene oxide identical with embodiment 15, the difference is that, the shaping in the second catalyst bed is hollow
(volume average particle size is 200 μm of spheric catalyst to the shaping titanium-silicon molecular sieve TS-1 of Titanium Sieve Molecular Sieve equivalent, and density is
0.75g/cm3, wherein, the content of titanium-silicon molecular sieve TS-1 is 85 weight %, and the content of silica is 15 weight %) replace (i.e.,
Liquid mixture firstly flows through the hollow Titanium Sieve Molecular Sieve of shaping, again passes through shaping titanium-silicon molecular sieve TS-1).
Carry out 1500 it is small when reaction, at the end of reaction reaction temperature be 60 DEG C, the concentration of hydrogen peroxide is 48 weight %.Instead
Answer 2 it is small when and 1500 it is small when obtained result listed in table 2.
Embodiment 17
Using the method propylene oxide identical with embodiment 16, the difference is that, it is catalyzed in the first catalyst bed and second
Under conditions of the loadings of agent bed are constant, the internal diameter of the second catalyst bed is improved so that the internal diameter of the first catalyst bed
Ratio with the internal diameter of the second catalyst bed is 1：1.
Carry out 1100 it is small when reaction, at the end of reaction reaction temperature be 62 DEG C, the concentration of hydrogen peroxide is 52 weight %.Instead
Answer 2 it is small when and 1100 it is small when obtained result listed in table 2.
Embodiment 18
Using the method propylene oxide identical with embodiment 16, the difference is that, it is catalyzed in the first catalyst bed and second
Under conditions of the loadings of agent bed are constant, the internal diameter of the second catalyst bed is improved so that the internal diameter of the first catalyst bed
Ratio with the internal diameter of the second catalyst bed is 1：2.
Carry out 900 it is small when reaction, at the end of reaction reaction temperature be 64 DEG C, the concentration of hydrogen peroxide is 53 weight %.Instead
Answer 2 it is small when and 900 it is small when obtained result listed in table 2.
Embodiment 19
The present embodiment uses following two catalyst：
It is molded hollow Titanium Sieve Molecular Sieve：Volume average particle size is 600 μm of spheric catalyst, density 0.68g/cm3, its
In, the content of hollow Titanium Sieve Molecular Sieve is 90 weight %, and the content of silica is 10 weight %；
It is molded titanium-silicon molecular sieve TS-1：Volume average particle size is 600 μm of spheric catalyst, density 0.72g/cm3, its
In, the content of titanium-silicon molecular sieve TS-1 is 90 weight %, and the content of silica is 10 weight %.
Reacted in the fixed bed reactors of two series connection, wherein, the quantity of each catalyst reactor bed
It is 1 layer.On the basis of the flow direction of liquid material in the reactor, by the catalysis in the fixed bed reactors of upstream
Agent bed is known as the first catalyst bed, and the catalyst bed in the fixed bed reactors in downstream is known as the second catalyst
Bed, the filling shaping hollow titanium si molecular sieves in the first catalyst bed, the filling shaping titanium silicon in the second catalyst bed
The weight of molecular sieve TS-1, the loaded catalyst in the first catalyst bed and the loaded catalyst in the second catalyst bed
Amount is than being 4：1, the ratio of the internal diameter of the internal diameter of the first catalyst bed and the second catalyst bed is 2：1.
By propylene, hydrogen peroxide (in the form of the hydrogen peroxide of 20 weight % provide) as after the methanol mixing of solvent from positioned at
The bottom of the fixed bed reactors of upstream is sent into and flows through the first catalyst bed, and the liquid mixture of output subsequently enters next
In a fixed bed reactors and flow through the second catalyst bed.Wherein, the molar ratio of propylene and hydrogen peroxide is 1：1, propylene with
The molar ratio of methanol is 1：8, the weight (hourly) space velocity (WHSV) of propylene is 2h-1.Initial reaction temperature in two fixed bed reactors is 40
DEG C, it is 1.0MPa to control the pressure in two fixed bed reactors in reaction process.
The composition for the reaction mixture that continuous monitoring is exported from reactor in reaction process, when meeting condition 1 the 1st time
(that is, in propylene oxide selectivity StWith initial (reaction is measured by sampling when proceeding to 2 hours) propylene oxide selectivity S0Ratio
St/S0For 0.85≤St/S0<When 0.9), the reaction temperature (reaction temperature of two reactors is improved with 0.02-2 DEG C/day of amplitude
Remain identical) until propylene oxide selectivity S ' and initial epoxy propane selectivity S0Ratio S '/S0For 0.9≤S '/S0≤
When 1 (that is, when meeting condition 2), stop improving reaction temperature and remain at the temperature (that is, set-up procedure A) after rise；
When meeting condition 1 the 2nd and 3 time, the quality of hydrogen peroxide in liquid mixture is improved (by carrying with the amplitude in 0.02-5%/day
The concentration of hydrogen peroxide is realized in high hydrogen peroxide, the corresponding dosage for reducing hydrogen peroxide, to keep mole of hydrogen peroxide and propylene
Than constant) until when meeting condition 2, stop improving the quality of hydrogen peroxide in liquid mixture and remain the numerical value after rise
(that is, set-up procedure B), and so on (that is, set-up procedure B twice is carried out between set-up procedure A twice).
Carry out 1500 it is small when reaction, at the end of reaction reaction temperature be 49 DEG C, the concentration of hydrogen peroxide is 62 weight %.Instead
Answer 2 it is small when and 1500 it is small when obtained result listed in table 2.
Table 2
By embodiment 16 as can be seen that making liquid mixture first with relatively low apparent speed compared with embodiment 17 and 18
Then degree passes through the catalyst bed positioned at downstream, energy with higher superficial velocity again by the catalyst bed positioned at upstream
It is enough further to extend the single trip use service life of catalyst, while more preferable reaction effect can also be obtained, show the oxidation of higher
Agent effective rate of utilization and epoxide selectivities.
Embodiment 20
Following two catalyst are used in the present embodiment：
It is molded hollow Titanium Sieve Molecular Sieve：Volume average particle size is 900 μm of spheric catalyst, density 0.72g/cm3, its
In, the content of hollow Titanium Sieve Molecular Sieve is 75 weight %, and the content of silica is 25 weight %；
It is molded titanium-silicon molecular sieve TS-1：Volume average particle size is 900 μm of spheric catalyst, density 0.78g/cm3, its
In, the content of titanium-silicon molecular sieve TS-1 is 75 weight %, and the content of silica is 25 weight %.
Reacted in reducing fixed bed reactors, which has two catalyst beds, is existed with liquid material
On the basis of flow direction in reactor, the first catalyst bed will be known as positioned at the catalyst bed of upstream, downstream will be located at
Catalyst bed be known as the second catalyst bed, the filling shaping hollow titanium si molecular sieves in the first catalyst bed, the
Filling shaping titanium-silicon molecular sieve TS-1 in two catalyst beds, the hollow Titanium Sieve Molecular Sieve of shaping in the first catalyst bed and the
The weight ratio of shaping titanium-silicon molecular sieve TS-1 in two catalyst beds is 6：1, the internal diameter of the first catalyst bed is urged with second
The ratio of the internal diameter of agent bed is 4：1.
Using n-butene, as oxidant tert-butyl hydroperoxide (in the form of oxidizing agent solution provide, wherein, with third
For ketone as solvent, the initial concentration of tert-butyl hydroperoxide is 15 weight %) and as after the acetone mixing of solvent from fixed bed
The bottom of reactor is sent into and flows through catalyst bed.Wherein, the molar ratio of n-butene and tert-butyl hydroperoxide is 1：0.5,
The molar ratio of n-butene and solvent acetone (not including the acetone in oxidizing agent solution) is 1：4, the weight (hourly) space velocity (WHSV) of n-butene is 4h-1.Initial reaction temperature in two catalyst beds is 45 DEG C, controls the pressure in fixed bed reactors in reaction process
For 1.5MPa.
The composition for the reaction mixture that continuous monitoring is exported from reactor in reaction process, when meeting condition 1 the 1st time
(that is, in epoxy butane selectivity StWith initial (reaction is measured by sampling when proceeding to 2 hours) epoxy butane selectivity S0Ratio
St/S0For 0.85≤St/S0<When 0.9), the reaction temperature (reaction of two catalyst beds is improved with 0.02-2 DEG C/day of amplitude
Temperature remains identical) until epoxy butane selectivity S ' and initial epoxy butane selectivity S0Ratio S '/S0For 0.9≤S '/
S0When≤1 (that is, when meeting condition 2), stop improving reaction temperature and remain at temperature (that is, the set-up procedure after rise
A)；When meeting condition 1 the 2-4 times, the matter of tert-butyl hydroperoxide in liquid mixture is improved with the amplitude in 0.02-5%/day
Amount (is realized, the corresponding dosage for reducing oxidizing agent solution, to protect by the concentration for improving tert-butyl hydroperoxide in oxidizing agent solution
The molar ratio for holding n-butene and tert-butyl hydroperoxide is constant) until when meeting condition 2, stop improving tertiary fourth in liquid mixture
The quality of base hydrogen peroxide simultaneously remains the numerical value (that is, set-up procedure B) after rise, and so on (that is, in set-up procedure twice
Set-up procedure B three times is carried out between A).
Carry out 1500 it is small when reaction, at the end of reaction reaction temperature be 54 DEG C, tert-butyl hydroperoxide in oxidizing agent solution
The concentration of hydrogen is 46 weight %.React 2 it is small when and 1500 it is small when obtained oxidant effective rate of utilization and epoxy butane selectivity
Listed in table 3.
Table 3
Claims (16)
1. a kind of olefin oxidation method, this method are included under oxidation reaction condition, make a kind of liquid mixture and titanium silicon molecule
Haptoreaction, the liquid mixture contain alkene, at least one oxidant and optional at least one to sieve in the reactor
Solvent, the Titanium Sieve Molecular Sieve are seated in the catalyst bed of fixed bed reactors, and the catalyst bed is urged including first
Agent bed and the second catalyst bed, the liquid mixture flow successively through first catalyst bed and described second and urge
Agent bed, the Titanium Sieve Molecular Sieve of first catalyst bed filling are hollow Titanium Sieve Molecular Sieve, the hollow titanium silicon molecule
The crystal grain of sieve is hollow-core construction, and the radical length of the chamber portion of the hollow-core construction is 5-300 nanometers, and the Titanium Sieve Molecular Sieve exists
25℃、P/P0=0.10, the benzene adsorbance measured under conditions of when adsorption time is 1 small is at least 70 milligrams per grams, the titanium silicon point
There are hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of son sieve；And second catalyst bed
The Titanium Sieve Molecular Sieve of filling is titanium-silicon molecular sieve TS-1,
Wherein, this method further includes the set-up procedure at least carried out once, and the set-up procedure is carried out in the condition 1 of satisfaction, with
Desirable oxidation selectivity of product is improved until meeting to stop the set-up procedure during condition 2,
Condition 1, sometime the desirable oxidation selectivity of product S under ttWith initial target oxidation product selectivity S0Ratio St/
S0For 0.85≤St/S0<1；
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S0Ratio S '/S0For 0.9≤S '/
S0≤1；
The set-up procedure is the combination of set-up procedure A or set-up procedure A and set-up procedure B,
Set-up procedure A：Improve the catalytic temperature；
Set-up procedure B：Improve the quality of oxidant in the liquid mixture.
2. according to the method described in claim 1, wherein, in the condition 1 of satisfaction, be adjusted step A or set-up procedure B,
And set-up procedure A at least once is carried out between the adjacent B of set-up procedure twice, or carried out between the adjacent A of set-up procedure twice to
A few set-up procedure B.
3. method according to claim 1 or 2, wherein, in condition 1, St/S0<0.9。
4. according to the method described in claim 1, wherein, catalytic temperature is improved with 0.01-2 DEG C/day of amplitude；With/
Or
The quality of oxidant in the liquid mixture is improved with the amplitude in 0.02-5%/day.
5. according to the method described in claim 1, wherein, the Titanium Sieve Molecular Sieve of the first catalyst bed filling and described the
The weight ratio of the Titanium Sieve Molecular Sieve of two catalyst beds filling is 0.1-20：1.
6. according to the method described in claim 5, wherein, the Titanium Sieve Molecular Sieve of the first catalyst bed filling and described the
The weight ratio of the Titanium Sieve Molecular Sieve of two catalyst beds filling is 2-10：1.
7. according to the method described in any one in claim 1,5 and 6, wherein, the liquid mixture flows through the first catalysis
The superficial velocity of agent bed is v1, the superficial velocity for flowing through the second catalyst bed is v2, v1＜ v2。
8. according to the method described in claim 7, wherein, v2/v1=1.5-15.
9. according to the method described in claim 8, wherein, v2/v1=2-5.
10. according to the method described in claim 7, wherein, during stop of the liquid mixture in the catalyst bed
Between be T, the residence time in first catalyst bed is T1, T1/ T=0.2-0.95.
11. according to the method described in claim 10, wherein, T1/ T=0.5-0.85.
12. according to the method described in any one in claim 1,2 and 4-6, wherein, the catalytic temperature is in 0-
In the range of 120 DEG C.
13. according to the method described in any one in claim 1,2 and 4-6, wherein, the molar ratio of the oxidant and alkene
In 0.1-10：In the range of 1.
14. according to the method described in any one in claim 1,2 and 4-6, the alkene is propylene and/or butylene.
15. according to the method described in any one in claim 1,2 and 4-6, the oxidant is peroxide.
16. according to the method for claim 15, wherein, the oxidant is selected from hydrogen peroxide, organic peroxide and mistake
Acid.
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| CN101941955A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing epoxypropane by using hydrogen peroxide and propylene |
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| CN101279959A (en) * | 2008-05-21 | 2008-10-08 | 湖南长岭石化科技开发有限公司 | Method for synthesizing epoxypropane |
| CN101941955A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing epoxypropane by using hydrogen peroxide and propylene |
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