CN105524020A - Oxidation method for olefin - Google Patents
Oxidation method for olefin Download PDFInfo
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- CN105524020A CN105524020A CN201410513915.2A CN201410513915A CN105524020A CN 105524020 A CN105524020 A CN 105524020A CN 201410513915 A CN201410513915 A CN 201410513915A CN 105524020 A CN105524020 A CN 105524020A
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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
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Abstract
The invention discloses an oxidation method for olefin. The method comprises the step of subjecting a liquid mixture and a titanium-silicate molecular sieve to contacting under the condition of oxidation reaction, wherein the liquid mixture comprises olefin, at least one oxidant, and at least one optional solvent; and when selectivity of a target oxidation product is lower than an expected value, the method also comprises the steps of improving a feeding temperature of the liquid mixture and optionally improving the quality of the oxidant in the liquid mixture. The method provided by the invention can maintain the selectivity of the target oxidation product at a high level for a long time, effectively prolong the single-way service life of the titanium-silicon molecular sieve used as a catalyst, and reduce regeneration frequency of the catalyst.
Description
Technical field
The present invention relates to a kind of olefin oxidation method.
Background technology
Epoxide is the important oxygen-containing organic compound of a class.Such as, propylene oxide is a kind of important basic organic chemical industry raw material, and in acryloyl derivative, output is only second to polypropylene.The maximum purposes of propylene oxide produces polyether glycol, with further processing and manufacturing urethane, also can be used for producing broad-spectrum propylene glycol.In addition, propylene oxide also can be used for the production of tensio-active agent, oil field demulsifier etc.
Along with the widespread use of the materials such as urethane, the demand of propylene oxide rises year by year.But still there is drawback in the technique of current industrial production propylene oxide, especially cannot meet the requirement of green chemistry chemical technology.Therefore, in the urgent need to developing not only economy but also environment amenable propylene oxide production process.
HTS appear as alkene epoxidation, phenol hydroxylation, keto-alcohol oxidation etc. open up a new way, particularly in alkene epoxidation, achieve good catalytic oxidation effect.Such as, Dow/BASF and Degussa/Uhde will be oxygenant with hydrogen peroxide, take methyl alcohol as solvent, under HTS exists, push the technique of synthesis of propylene oxide by propylene oxidation to industrialization.
When adopting HTS as catalyzer, ubiquitous problem is, device operates after for some time, and the activity and selectivity of catalyzer can reduce, and namely catalyzer there will be deactivation phenomenom in operation process.At present main settling mode decaying catalyst is carried out in-situ regeneration or ex-situ regeneration to make renewing catalyst activity.Wherein, in-situ regeneration, mainly for the lighter situation of catalyst inactivation, is generally and adopts solvent and/or oxygenant to carry out dipping or the flushing of for some time to decaying catalyst at a certain temperature; Ex-situ regeneration, mainly for the more serious situation of catalyst inactivation, is generally carry out roasting to decaying catalyst.Industrial, general employing first makes renewing catalyst activity through in-situ regeneration, when in-situ regeneration cannot make catalyst activity recover, then adopts ex-situ regeneration.
But when the catalyzer of regeneration puts into operation again, when particularly again putting into operation after in-situ regeneration, the activity and selectivity fluctuation of catalyzer is comparatively large, needs could stablize for a long time; Meanwhile, also need to combine and improve the smooth running that the operation such as temperature of reaction carrys out realization response, but like this can further accelerator activator inactivation reduce desirable oxidation selectivity of product, affect subsequent product refining spearation, be also unfavorable for keeping the safety in production.
Therefore, the work-ing life of extending catalyst, particularly one way work-ing life, thus the regeneration frequency reaction system remained using HTS as catalyzer reducing catalyzer needs the technical problem of solution badly.
Summary of the invention
The object of the present invention is to provide a kind of method of olefin oxide, the method can extend the one way work-ing life of the HTS as catalyzer effectively.
The invention provides a kind of olefin oxidation method, the method comprises makes a kind of liquid mixture and HTS contact reacts in the reactor, described liquid mixture contains alkene, at least one oxygenant and optional at least one solvent, wherein, the method also comprises the set-up procedure of at least carrying out once, satisfy condition 1 time carry out described set-up procedure, to improve desirable oxidation selectivity of product until satisfy condition 2 time stop described set-up procedure
Desirable oxidation selectivity of product S under condition 1, sometime t
twith initial target oxidation products selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S
0ratio S '/S
0be 0.9≤S '/S
0≤ 1;
Described 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 temperature improving described liquid mixture;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
According to olefin oxidation method of the present invention, in long-time continuous operational process, when the desirable oxidation selectivity of product that the reaction mixture exported by reactor is determined is lower than desired value, carry out set-up procedure, namely improve as the temperature of the liquid mixture of charging and the quality of oxygenant in improving as charging liquid mixture alternatively, the desirable oxidation selectivity of product originally presenting downtrending can be made to go up.In long-time continuous operational process, desirable oxidation selectivity of product can be maintained higher level all the time like this, avoid needing in later separation purge process to adjust operational condition according to the composition of reaction mixture on the one hand; Then effectively extend the one way work-ing life of the HTS as catalyzer on the other hand, reduce the regeneration frequency of catalyzer, extend the parallel-adder settle-out time of device.
Embodiment
The invention provides a kind of olefin oxidation method, the method comprises makes a kind of liquid mixture and HTS contact reacts in the reactor, described liquid mixture contains alkene, at least one oxygenant and optional at least one solvent, wherein, the method also comprises the set-up procedure of at least carrying out once, satisfy condition 1 time carry out described set-up procedure, to improve desirable oxidation selectivity of product until satisfy condition 2 time stop described set-up procedure
Desirable oxidation selectivity of product S under condition 1, sometime t
twith initial target oxidation products selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S
0ratio S '/S
0be 0.9≤S '/S
0≤ 1;
Described 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 temperature improving described liquid mixture;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
In the present invention, " at least one " represents one or more (as two or more); " optionally " represents containing or does not contain.
According to method of the present invention, satisfy condition 2 time, stop improve as the liquid mixture of charging temperature and the temperature of liquid mixture is remained the temperature after rising; When method of the present invention also comprises set-up procedure B, satisfy condition 2 time, stop improving the quality of oxygenant in liquid mixture and the quality of oxygenant remained numerical value when satisfying condition 2.
Described set-up procedure is carried out when meeting above-mentioned condition 1, the desirable oxidation selectivity of product originally presenting downtrending can be made to go up, desirable oxidation selectivity of product is promoted to higher level, thus extend the one way work-ing life of HTS, and desirable oxidation selectivity of product is maintained higher level for a long time.
Under the prerequisite in one way work-ing life that can extend HTS, from the angle of further extension fixture parallel-adder settle-out time, in condition 1, S
t/ S
0<0.9.
In the present invention, the desirable oxidation selectivity of product=mole number of the alkene of the mole number/participation reaction of desirable oxidation product (in the reaction mixture obtained) × 100%;
Wherein, the mole number of the alkene in the reaction mixture of the mole number of the alkene of the mole number=add of the alkene of reaction-obtain is participated in.
Desirable oxidation selectivity of product S can be determined by the composition of monitoring the reaction mixture exported from reactor in reaction process continuously
0, S
tand S '.When reactor is multiple reactor, with the flow direction of liquid mixture for benchmark, the reaction mixture exported by the reactor being positioned at logistics end is to determine desirable oxidation selectivity of product S
0, S
tand S '.
In the present invention, initial target oxidation products selectivity S
0after reactor steady running, determine from the composition of the first batch of reaction mixture of reactor output.Such as, the reaction mixture that reactor steady running can be obtained within 0.5-10 hour is as first batch of reaction mixture.
Ordinary method can be adopted to measure the composition of the reaction mixture exported from reactor, such as vapor-phase chromatography.
Although satisfy condition 1 time, improve the temperature of liquid mixture and improve the quality of oxygenant in liquid mixture alternatively until satisfy condition 2, but in set-up procedure A, preferably with the amplitude of 0.01-5 DEG C/day, the temperature more preferably improving liquid mixture with the amplitude of 0.02-2 DEG C/day; In set-up procedure B, preferably improve the quality of oxygenant in liquid mixture with the amplitude in 0.02-5%/sky, longer HTS one way work-ing life can be obtained like this, reaction can also be made to carry out more reposefully.In the present invention, in the present invention, " amplitude " refers to the step-length between adjacent two numerical value.According to method of the present invention, in whole reaction process, in liquid mixture, the mol ratio of oxygenant and alkene is preferably not higher than 10:1, is more preferably not higher than 5:1, further preferably not higher than 3:1.
According to method of the present invention, the temperature (that is, feeding temperature) of described liquid mixture is not preferably higher than 120 DEG C.The initial temperature of described liquid mixture is generally more than 0 DEG C.From the optionally angle improved further for epoxide, the initial temperature of described liquid mixture preferably in the scope of 20-80 DEG C, more preferably in the scope of 30-60 DEG C.
According to method of the present invention, various method can be adopted to improve the quality of oxygenant in liquid mixture.Such as: the addition of oxygenant during preparation described liquid mixture can be improved to improve the quality of oxygenant in liquid mixture.When oxygenant provides in the form of a solution, also the quality of oxygenant in liquid mixture can be improved by the mode of the concentration improving oxygenant in oxidizing agent solution, now the consumption of oxidizing agent solution can remain unchanged (now, the research on maximum utilized quantity of oxygenant makes the mol ratio of oxygenant and alkene not higher than 10:1, more preferably no higher than 5:1, further preferably not higher than 3:1), also can correspondingly carry out adjusting (such as, the consumption of corresponding reduction oxidizing agent solution, to keep the constant rate between alkene and oxygenant), as long as can guarantee that the quality of oxygenant in liquid mixture is for improving.In actual mechanical process, at least part of solvent can be mixed with oxygenant, thus preparation oxidizing agent solution, realize reaction is carried out in the presence of at least one solvent simultaneously.
According to method of the present invention, in long-time continuous operational process, the increase rate of liquid mixture temperature and the increase rate of optional oxygenant quality can be identical or different.Usually, the amplitude that early stage can be lower in the reaction improves liquid mixture temperature and optional oxygenant quality, and the phase can improve liquid mixture temperature and optional oxygenant quality with higher amplitude after the reaction.
According to method of the present invention, when carrying out set-up procedure, all the other conditions are generally and remain unchanged, and can certainly correspondingly adjust.
According to method of the present invention, described 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 can be used alone, that is, satisfy condition 1 time, only can carry out set-up procedure A.
Set-up procedure A also can combinationally use with set-up procedure B.
When set-up procedure A and set-up procedure B is combinationally used, in a first embodiment, satisfy condition 1 time, carry out set-up procedure A and set-up procedure B, now set-up procedure A and set-up procedure B can synchronously carry out, and also can asynchronously carry out, and preferably asynchronously carries out, so more be conducive to operation, be also easier to control reaction simultaneously.
When set-up procedure A and set-up procedure B is combinationally used, in the second embodiment, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, set-up procedure A is at least one times carried out, as 1-5 (preferred 1-3 time) set-up procedure A between adjacent twice set-up procedure B.That is, 1 is satisfied condition for n time altogether, wherein, n
1secondary satisfy condition 1 time, carry out set-up procedure A, n
2secondary satisfy condition 1 time, carry out set-up procedure B, n
1+ n
2=n, n
1>=n
2, as n
1/ n
2=1-5, preferred n
1/ n
2=1-3.
When set-up procedure A and set-up procedure B is combinationally used, in the third embodiment, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, set-up procedure B is at least one times carried out, as 1-5 (preferred 1-3 time) set-up procedure B between adjacent twice set-up procedure A.That is, n ' is secondary altogether satisfies condition 1, wherein, and n
1' secondary satisfy condition 1 time, carry out set-up procedure B, n
2' secondary satisfy condition 1 time, carry out set-up procedure A, n
1'+n
2'=n ', n
1'>=n
2', as n
1'/n
2'=1-5, preferred n
1'/n
2'=1-3.
Preferably, set-up procedure A and set-up procedure B is combinationally used, like this can one way work-ing life of more effectively extending catalyst, obtain higher desirable oxidation selectivity of product.
According to method of the present invention, described oxygenant can be that commonly use various can by the material of olefin oxidation.Preferably, described oxygenant is superoxide.Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, organo-peroxide and peracid.Described organo-peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.The concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
The consumption of described oxygenant can be selected according to the oxidation products of expection, is not particularly limited.Usually, the mol ratio of described alkene and described oxygenant can in the scope of 0.1-10:1, preferably in the scope of 0.2-5:1, more preferably in the scope of 0.3-3:1.
According to method of the present invention, may be used for being oxidized multiple alkene.Described alkene can be C
2-C
16alkene.Described alkene can be monoolefine, also can be polyene hydrocarbon, is preferably monoolefine.Particularly, described alkene is propylene and/or butylene (as 1-butylene).
According to method of the present invention, described liquid mixture can contain solvent, also can not contain solvent.Preferably, described liquid mixture contains at least one solvent, can control speed and the severe degree of reaction so better.The present invention is not particularly limited for the kind of described solvent, and described solvent can be all kinds of SOLVENTS conventional in olefin hydrocarbon oxidation reaction.Particularly, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone, C
2-C
10nitrile and C
1-C
6carboxylic acid at least one.Preferably, described solvent is C
1-C
6alcohol, C
3-C
8ketone and C
2-C
5nitrile in one or more.More preferably, described solvent is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol and acetone.Further preferably, described solvent is one or more in methyl alcohol, acetone and the trimethyl carbinol.The kind of the solvent in described solvent and oxidizing agent solution can be identical or different, is not particularly limited.
The present invention is not particularly limited for the consumption of described solvent, can select according to the amount of alkene and oxygenant.Usually, the mol ratio of described solvent and described alkene can be 1-100:1, is preferably 2-80:1, is more preferably 10-50:1.
According to method of the present invention, according to specific needs, described liquid mixture can also contain at least one alkaline matter, with the pH value of described liquid mixture is adjusted to be in 6.5-9 scope within, the selectivity for epoxide can be improved so further.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, as sodium, potassium, magnesium or calcium; N is and M
1the identical integer of valency).
According to method of the present invention, adopt the catalyzer that HTS is reacted as alkene and oxidising agent.Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).Described HTS is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure, the HTS of two-dimentional hexagonal structure and BEA structure, is more preferably the HTS of MFI structure.
According to method of the present invention, described HTS is preferably hollow HTS, can obtain better catalytic effect like this.Described hollow HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, the contact form of described HTS and described liquid mixture is not particularly limited, can HTS be seated in the beds of fixed-bed reactor, make described liquid mixture by described beds, thus realize, under HTS exists, alkene and oxidising agent being reacted; Also described liquid mixture and HTS can be mixed to form slurry, thus realize, under HTS exists, alkene and oxidising agent being reacted.
When described liquid mixture and HTS are mixed to form slurry, can adopt various method that slurry is carried out solid-liquor separation after contact reacts completes, thus obtain the liquid material containing desirable oxidation product.Such as: by membrane separation unit, described liquid material can be carried out solid-liquor separation.
Time in the beds described HTS being seated in fixed-bed reactor, the quantity of described beds can be one or more.When the quantity of beds is multiple, the different zones of a reactor can be positioned at, also can be arranged in multiple reactor.
In one embodiment of the invention, described beds contains the first beds and the second beds, described liquid mixture flows through the first beds and the second beds successively, namely with the flow direction of described liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds.Described first beds can, for identical, also can be different with the kind of the HTS of loading in described second beds.Preferably, the HTS of described first beds filling is hollow HTS, the HTS of described second beds filling is the HTS except hollow HTS, as one or more in the HTS (such as HTS Ti-MCM-41) of the HTS (such as titanium-silicon molecular sieve TS-1) of other MFI structure, two-dimentional hexagonal structure and the HTS (such as HTS Ti-Beta) of BEA structure, the deactivation rate of HTS can be delayed so further.More preferably, the HTS of described first beds filling is hollow HTS, the HTS of described second beds filling is titanium-silicon molecular sieve TS-1, can obtain better catalytic effect like this, and extend the one way work-ing life of HTS further.
When described beds contains the first beds and the second beds, the weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds can be 0.1-20:1.The weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds is preferably more than 0.5, is more preferably more than 1, and more preferably more than 2.The weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds is preferably less than 15, is more preferably less than 10.Still more preferably, the weight ratio of the HTS of loading in the HTS of loading in described first beds and described second beds is 2-10:1.
When described beds contains the first beds and the second beds, described first beds and the second beds can contain one or more beds separately.When the first beds and/or the second beds contain multiple beds, can for being connected in series between multiple beds, also can for being connected in parallel, can also be series connection and combination in parallel, such as: multiple beds is divided into many groups, beds often in group for being connected in series and/or being connected in parallel, for being connected in series and/or being connected in parallel between each group.Described first beds and described second beds can be arranged on the different zones of same reactor, also can be arranged in different reactors.
When described beds contains the first beds and the second beds, it can, for identical, also can be different that described liquid mixture flows through the first beds with the superfacial velocity of the second beds.Preferably, described liquid mixture flows through the superfacial velocity of the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1< v
2, the one way work-ing life of HTS can be extended so further, higher oxygenant effective rate of utilization and desirable oxidation selectivity of product can also be obtained simultaneously.More preferably, v
2/ v
1=1.5-15.V
2/ v
1be preferably more than 2.V
2/ v
1be preferably less than 10, be more preferably less than 5.Further preferably, v
2/ v
1=2-5.
In the present invention, described superfacial velocity (flow velocity) to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m
2meter) ratio.The quality of the liquid mixture of fixed-bed reactor can will be sent into as " by the mass rate of the liquid mixture of whole beds in the unit time " in unit time.In the present invention, particular requirement be there is no for the superfacial velocity of liquid mixture in the first beds, generally can at 0.001-200kg/ (m
2s) in scope.
Various method can be adopted to regulate the superfacial velocity of described liquid mixture in the first beds and the second beds.Such as, the superfacial velocity of regulates liquid mixture can be carried out by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of described first beds can be made to be greater than the cross-sectional area of described second beds, thus to make v
1< v
2.Particularly, the internal diameter of described first beds is D
1, the internal diameter of described second beds is D
2, wherein, D
1> D
2.Preferably, D
1/ D
2=1.5-15.D
1/ D
2be more preferably more than 2.D
1/ D
2be more preferably less than 10, more preferably less than 5.Still more preferably, D
1/ D
2=2-5.
When described beds contains the first beds and the second beds, the residence time of described liquid mixture in the first beds is T
1, the total residence time in beds is T, preferably, and T
1/ T=0.2-0.95, can obtain the catalyzer one way work-ing life extended further like this, can also obtain better reaction effect simultaneously.T
1/ T is preferably more than 0.3, is more preferably more than 0.5.T
1/ T is preferably less than 0.9, is more preferably less than 0.85.Further preferably, T
1/ T=0.5-0.85.
According to method of the present invention, when beds contains the first beds and the second beds, material can be supplemented as the case may be between the first beds and the second beds, when the first beds and/or the second beds are multiple beds, fresh material can be supplemented between the first beds and/or between the second beds in described liquid mixture as the case may be.Such as: between the first beds and the second beds, between the first beds and/or between the second beds, supplement alkene, oxygenant and/or solvent.But, it should be noted that, (namely described liquid mixture flows through whole beds of the first beds, the whole process of the first beds) and the second beds whole beds (namely, the whole process of the second beds), described liquid mixture not included in the fresh material introduced between the first beds, between the second beds and between the first beds and the second beds, previously described superfacial velocity is determined by described liquid mixture, is not subject to the impact whether introducing fresh material.
According to method of the present invention, beds only can load HTS, also can contain HTS and inactive filler.In beds, load inactive filler to adjust the amount of HTS in beds, thus the speed of reaction is regulated.When described beds contains HTS and inactive filler, in beds, the content of inactive filler can be 5-95 % by weight.Described inactive filler refers to the filler not having or substantially do not have catalytic activity to oxidizing reaction, and its specific examples can include but not limited to: one or more in quartz sand, ceramic ring and potsherd.
According to method of the present invention, described HTS can be the former powder of HTS, also can be shaping HTS, is preferably shaping HTS.Shaping HTS is generally containing the HTS as activeconstituents and the carrier as binding agent, and wherein, the content of HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 70-90 % by weight; The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 10-30 % by weight.The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.Particularly, the median size of described shaping HTS can be 4-10000 micron, is preferably 5-5000 micron, is more preferably 40-4000 micron, as 50-1000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
According to method of the present invention, described HTS is as catalyzer, and its consumption is as the criterion can realize catalysis, is not particularly limited.Can select according to the contact form of HTS and described liquid mixture.Such as, when HTS and described liquid mixture are mixed to form slurry, the weight ratio of alkene and HTS can be 0.1-50:1, is preferably 1-50:1, as 1-25:1; Time in beds HTS being seated in fixed-bed reactor, the weight hourly space velocity of described alkene can be 0.1-20h
-1, be preferably 1-10h
-1.In the present invention, weight hourly space velocity with the total amount of HTS in whole beds for benchmark.
According to method of the present invention, the temperature of beds generally can in the scope of 0-120 DEG C, preferably in the scope of 20-80 DEG C, more preferably in the scope of 20-60 DEG C.When described beds contains the first beds and the second beds, described first beds can be identical with the reaction conditions of the second beds, also can be different.From the angle of ease-to-operate, described first beds is identical with the reaction conditions between the second beds.
According to method of the present invention, the pressure in reactor can be selected as the case may be.Usually, in gauge pressure, the pressure in reactor can in the scope of 0-5MPa, preferably in the scope of 0.1-3MPa.
Can also comprise according to method of the present invention and the reaction mixture exported from fixed-bed reactor is separated, to obtain desirable oxidation product (as epoxide) and unreacted reactant.The method being carried out being separated by reaction mixture can be selected for the routine of this area, is not particularly limited.Isolated unreacted reactant can recycle.
Adopt method of the present invention by olefin oxidation, effectively can extend the one way work-ing life of the HTS as catalyzer, reduce the regeneration frequency of HTS.Method of the present invention is specially adapted to olefin oxidation to prepare epoxide, adopts method of the present invention can obtain the comparatively stable reaction mixture of epoxide content, is convenient to the separation and purification of subsequent products.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, the method preparation described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight; Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight; HTS Ti-MCM-41 used is that prepared by the method described in 1994,147-148, its titanium oxide content is 3 % by weight according to Corma etc. at Chem.Commun.; HTS Ti-Beta used is that prepared by the method described in 1997,677-678, its titanium oxide content is 2.6 % by weight according to TakashiTatsumi etc. at J.Chem.Soc.Chem.Commun..
In following examples and comparative example, agents useful for same is commercially available analytical reagent, and pressure is all in gauge pressure.
In following examples and comparative example, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant effective rate of utilization, epoxide selectivities and by product selectivity on this basis respectively:
Oxygenant effective rate of utilization=(mole number of the oxygenant of the mole number/participation reaction of the epoxide that reaction generates) × 100%;
Epoxide selectivities=the mole number of the alkene of the mole number/participation reaction of epoxide (in the reaction mixture obtained) × 100%;
By product selectivity (ppm)=(mole number of the alkene of mole number/reaction consumption of the by product that reaction generates) × 1000000.
Embodiment 1-20 is for illustration of method of the present invention.
Embodiment 1
By catalyzer, (that is, shaping titanium-silicon molecular sieve TS-1, volume average particle size is the spherical catalyst of 500 μm, and in catalyzer, the content of titanium-silicon molecular sieve TS-1 is 80 % by weight, and the content of silicon oxide is 20 % by weight, and density is 0.76g/cm
3) be seated in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer.
The liquid mixture formed by propylene, the hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) as oxygenant, the methyl alcohol as solvent and ammoniacal liquor (concentration is 25 % by weight) is sent into from the bottom of fixed-bed reactor and flows through beds.Wherein, the mol ratio of propylene and hydrogen peroxide is 3:1, and the mol ratio of propylene and solvent methanol is 1:20, and the consumption of ammoniacal liquor makes the pH value of liquid mixture be 8, and the weight hourly space velocity of propylene is 4h
-1.The initial charge temperature of liquid mixture is 30 DEG C, and by the heater strip be arranged in beds, beds being heated to temperature is 30 DEG C, in reaction process, and the heating condition of heater strip remains unchanged.Pressure in fixed-bed reactor is 2.0MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at propylene oxide selectivity S in reaction process
twith initial (reaction proceeds to 0.5 little sampling and measuring constantly) propylene oxide selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0during <0.9 (that is, satisfy condition 1 time), improve the temperature of liquid mixture until propylene oxide selectivity S ' and initial epoxy propane selectivity S with the amplitude of 0.02-2 DEG C/day
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving the temperature of liquid mixture and the temperature after being remained rising.
Carry out the reaction of 760 hours, at the end of reaction, the feeding temperature of liquid mixture is 52 DEG C.Oxygenant effective rate of utilization, propylene oxide selectivity and the selectivity as the acetone of by product that the reaction mixture being proceeded to 0.5 hour by reaction and obtained for 760 hours is determined are listed in Table 1.
Comparative example 1
Adopt the method propylene oxide identical with embodiment 1, unlike, do not change the feeding temperature of liquid mixture in reaction process.
The result of reacting 0.5 hour and 400 hours is listed in Table 1.
Embodiment 2
Adopt the method propylene oxide identical with embodiment 1, unlike, in reaction process, to satisfy condition for the 1st time 1 time, with the amplitude of 0.02-2 DEG C/day improve liquid mixture temperature until satisfy condition 2 time, stop improving the temperature of liquid mixture the temperature after being remained rising; To satisfy condition for the 2nd time 1 time, the quality improving hydrogen peroxide in liquid mixture with the amplitude in 0.02-2%/sky (is realized by the concentration improving hydrogen peroxide in hydrogen peroxide, the consumption of corresponding reduction hydrogen peroxide, to keep the mol ratio of hydrogen peroxide and propylene constant) until satisfy condition 2 time, stop improving the quality of hydrogen peroxide in liquid mixture and the numerical value after remaining rising, the rest may be inferred (namely, odd-times satisfy condition 1 time, improve the temperature of liquid mixture until satisfy condition 2 with the amplitude of 0.02-2 DEG C/day; Even-times satisfy condition 1 time, improve the concentration of hydrogen peroxide in liquid mixture until satisfy condition 2 with the amplitude in 0.02-0.05%/sky).
Carry out the reaction of 860 hours, at the end of reaction, the feeding temperature of liquid mixture is 44 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 45 % by weight.The result of reacting 0.5 hour and 860 hours is listed in Table 1.
Embodiment 3
Adopt the method propylene oxide identical with embodiment 2, unlike, (that is, shaping hollow HTS, the density of catalyzer is 0.70g/cm in the hollow HTS replacement of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer
3).
Carry out the reaction of 860 hours, at the end of reaction, the feeding temperature of liquid mixture is 41 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 39 % by weight.The result of reacting 0.5 hour and 860 hours is listed in Table 1.
Embodiment 4
Adopt the method propylene oxide identical with embodiment 2, unlike, (that is, shaping HTS Ti-MCM-41, the density of catalyzer is 0.68g/cm in the HTS Ti-MCM-41 replacement of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer
3).
Carry out the reaction of 780 hours, at the end of reaction, the feeding temperature of liquid mixture is 45 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 46 % by weight.The result of reacting 0.5 hour and 780 hours is listed in Table 1.
Embodiment 5
Adopt the method propylene oxide identical with embodiment 2, unlike, (that is, shaping HTS Ti-Beta, the density of catalyzer is 0.78g/cm in the HTS Ti-Beta replacement of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer
3).
Carry out the reaction of 780 hours, at the end of reaction, the feeding temperature of liquid mixture is 44 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 44 % by weight.The result of reacting 0.5 hour and 780 hours is listed in Table 1.
Embodiment 6
Adopt the method propylene oxide identical with embodiment 2, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS (identical with embodiment 3), recharge shaping titanium-silicon molecular sieve TS-1 (identical with embodiment 1), thus formation beds, i.e. the beds of liquid mixture first by being formed by shaping hollow HTS, then the beds by being formed by shaping titanium-silicon molecular sieve TS-1.Wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 2:1.
Carry out the reaction of 1160 hours, at the end of reaction, the feeding temperature of liquid mixture is 40 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 41 % by weight.The result of reacting 0.5 hour and 1160 hours is listed in Table 1.
Embodiment 7
Adopt the method propylene oxide identical with embodiment 6, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping titanium-silicon molecular sieve TS-1, to recharge shaping hollow HTS, thus formation beds, wherein, the weight ratio of shaping titanium-silicon molecular sieve TS-1 and shaping hollow HTS is 1:2.
Carry out the reaction of 800 hours, at the end of reaction, the feeding temperature of liquid mixture is 46 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 46 % by weight.The result of reacting 0.5 hour and 800 hours is listed in Table 1.
Embodiment 8
Adopt the method propylene oxide identical with embodiment 6, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS, recharge shaping titanium-silicon molecular sieve TS-1, thus formation beds, wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:1.
Carry out the reaction of 920 hours, at the end of reaction, the feeding temperature of liquid mixture is 45 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 44 % by weight.The result of reacting 0.5 hour and 920 hours is listed in Table 1.
Embodiment 9
Adopt the method propylene oxide identical with embodiment 6, unlike, under the condition that the total filling amount of shaping HTS is constant, first load shaping hollow HTS, recharge shaping titanium-silicon molecular sieve TS-1, wherein, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:2.
Carry out the reaction of 890 hours, at the end of reaction, the feeding temperature of liquid mixture is 45 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 43 % by weight.The result of reacting 0.5 hour and 890 hours is listed in Table 1.
Embodiment 10
Adopt the method propylene oxide identical with embodiment 6, unlike, under the condition that the total filling amount of shaping HTS is constant, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 8:1.
Carry out the reaction of 1160 hours, at the end of reaction, the feeding temperature of liquid mixture is 42 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 40 % by weight.The result of reacting 0.5 hour and 1160 hours is listed in Table 1.
Embodiment 11
Adopt the method propylene oxide identical with embodiment 6, unlike, under the condition that the total filling amount of shaping HTS is constant, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 20:1.
Carry out the reaction of 1040 hours, at the end of reaction, the feeding temperature of liquid mixture is 45 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 43 % by weight.The result of reacting 0.5 hour and 1040 hours is listed in Table 1.
Embodiment 12
Adopt the method propylene oxide identical with embodiment 10, unlike, the shaping HTS Ti-MCM-41 (identical with embodiment 4) of shaping titanium-silicon molecular sieve TS-1 equivalent replaces.
Carry out the reaction of 880 hours, at the end of reaction, the feeding temperature of liquid mixture is 47 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 45 % by weight.The result of reacting 0.5 hour and 880 hours is listed in Table 1.
Embodiment 13
Adopt the method propylene oxide identical with embodiment 10, unlike, the shaping HTS Ti-Beta (identical with embodiment 5) of shaping titanium-silicon molecular sieve TS-1 equivalent replaces.
Carry out the reaction of 880 hours, at the end of reaction, the feeding temperature of liquid mixture is 46 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 43 % by weight.The result of reacting 0.5 hour and 880 hours is listed in Table 1.
Table 1
Embodiment 1 and 2 and comparative example 1 are compared and can find out, adopts method of the present invention desirable oxidation selectivity of product stably can be maintained higher level within the longer time, thus effectively extend the one way work-ing life of HTS.
Embodiment 1 and embodiment 2 are compared and can find out, using the feeding temperature of the raising liquid mixture as set-up procedure and the mass combination use improving oxygenant in liquid mixture, the one way work-ing life of the HTS as catalyzer can be extended further.
Embodiment 14-19 relates to following two kinds of catalyzer.
C1: (for volume average particle size is the spherical catalyst of 1000 μm, density is 0.72g/cm to shaping hollow HTS
3), this catalyzer contains the hollow HTS of 75 % by weight and the silicon oxide of 25 % by weight.
C2: (for volume average particle size is the spherical catalyst of 1000 μm, density is 0.78g/cm to shaping titanium-silicon molecular sieve TS-1
3), this catalyzer contains the titanium-silicon molecular sieve TS-1 of 75 % by weight and the silicon oxide of 25 % by weight.
Embodiment 14
The reducing fixed-bed reactor that the present embodiment adopts have the beds for loading HTS of two different inner diameters, are the internal diameter zone of transition of taper between two beds, wherein not loading catalyst.With liquid material flow direction in the reactor for benchmark, the beds being positioned at upstream is called the first beds, the beds being positioned at downstream is called the second beds, first beds and the equal loading catalyst C1 of the second beds, the weight ratio of the loaded catalyst in the loaded catalyst in the first beds and the second beds is 5:1, and the ratio of the internal diameter of the first beds and the internal diameter of the second beds is 2:1.
Using by propylene, as oxygenant hydrogen peroxide (providing using the form of the hydrogen peroxide of 25 % by weight) and form liquid mixture as the methanol mixed of solvent, the bottom of described liquid mixture from fixed-bed reactor is sent into, flows through the first beds and the second beds successively.Wherein, the mol ratio of propylene and hydrogen peroxide is 1:0.5, and the mol ratio of propylene and solvent methanol is 1:50, and the weight hourly space velocity (with the total amount of the HTS in the first beds and the second beds for benchmark) of propylene is for 3h
-1.The initial charge temperature of liquid mixture is 35 DEG C, by the heater strip be arranged in the first beds and the second beds, the first beds and the second beds being heated to temperature is 35 DEG C, in reaction process, the heating condition of heater strip remains unchanged.Pressure-controlling in fixed-bed reactor is 1.5MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at propylene oxide selectivity S in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) propylene oxide selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0during <0.9 (that is, satisfy condition 1 time), improve the temperature of liquid mixture until propylene oxide selectivity S ' and initial epoxy propane selectivity S with the amplitude of 0.02-2 DEG C/day
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving the temperature of liquid mixture and the temperature after being remained rising.
Carry out the reaction of 860 hours, at the end of reaction, the feeding temperature of liquid mixture is 56 DEG C.By reacting propylene oxide selectivity that the reaction mixture that proceeds to 2 hours and obtain for 860 hours determines and listing in table 2 as the selectivity of by product acetone.
Embodiment 15
Adopt the method propylene oxide identical with embodiment 14, unlike, the initial molar ratio of propylene and hydrogen peroxide is 1:0.5, in reaction process, to satisfy condition for the 1st time 1 time, the quality of hydrogen peroxide in liquid mixture is improved (namely with the amplitude in 0.02-5%/sky, set-up procedure B) (realized by the concentration improving hydrogen peroxide in hydrogen peroxide, simultaneously the consumption of hydrogen peroxide remains unchanged) until satisfy condition 2 time, stop improving the quality of hydrogen peroxide and the numerical value after being remained rising; Satisfy condition the 2nd and 3 times 1 time, the feeding temperature of liquid mixture is improved (namely with the amplitude of 0.02-5 DEG C/day, set-up procedure A) until satisfy condition 2 time, top out the feeding temperature of liquid mixture the temperature after being remained rising, the rest may be inferred (that is, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, between adjacent twice set-up procedure B, twice set-up procedure A is carried out).
Carry out the reaction of 960 hours, at the end of reaction, the feeding temperature of liquid mixture is 48 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 40 % by weight.The result of reacting 2 hours and 960 hours is listed in table 2.
Embodiment 16
Adopt the method propylene oxide identical with embodiment 15, unlike, the catalyzer C2 of the catalyzer C1 equivalent in the second beds replaces.
Carry out the reaction of 1360 hours, at the end of reaction, the feeding temperature of liquid mixture is 48 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 39 % by weight.The result of reacting 2 hours and 1360 hours is listed in table 2.
Embodiment 17
Adopt the method propylene oxide identical with embodiment 16, unlike, under the condition that catalyzer total filling amount remains unchanged, make the weight ratio of catalyzer C1 and catalyzer C2 be 10:1, the first beds and the ratio of the internal diameter of the second beds are 5:1 (internal diameter of the second beds is identical with embodiment 18).
Carry out the reaction of 1360 hours, at the end of reaction, the feeding temperature of liquid mixture is 49 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 34 % by weight.The result of reacting 2 hours and 1360 hours is listed in table 2.
Embodiment 18
Adopt the method propylene oxide identical with embodiment 16, unlike, under the condition that the loadings of the first beds and the second beds is constant, the first beds and the ratio of the internal diameter of the second beds is made to be 1:1 (internal diameter of the second beds is identical with embodiment 16).
Carry out the reaction of 1260 hours, at the end of reaction, the feeding temperature of liquid mixture is 51 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 36 % by weight.The result of reacting 2 hours and 1260 hours is listed in table 2.
Embodiment 19
Adopt the method propylene oxide identical with embodiment 16, unlike, under the condition that the loadings of the first beds and the second beds is constant, the first beds and the ratio of the internal diameter of the second beds is made to be 1:2 (internal diameter of the second beds is identical with embodiment 16).
Carry out the reaction of 1060 hours, at the end of reaction, the feeding temperature of liquid mixture is 52 DEG C, and in hydrogen peroxide, the concentration of hydrogen peroxide is 38 % by weight.The result of reacting 2 hours and 1060 hours is listed in table 2
Table 2
Embodiment 16,18 and 19 is compared and can find out, make liquid mixture elder generation with lower superfacial velocity by being positioned at the beds of upstream, and then with higher superfacial velocity by being positioned at the beds in downstream, can one way work-ing life of extending catalyst further, better reaction effect can also be obtained simultaneously, demonstrate higher oxygenant effective rate of utilization and epoxide selectivities.
Embodiment 20
The catalyzer used in the present embodiment is shaping hollow HTS (for volume average particle size is the spherical catalyst of 600 μm), and this catalyzer contains the hollow HTS of 85 % by weight and the silicon oxide of 15 % by weight.
By catalyst loading in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer.
Using 1-butylene, as the tertbutyl peroxide of oxygenant, (form being hybridly prepared into oxidizing agent solution with acetonitrile provides, in oxidizing agent solution, the starting point concentration of tertbutyl peroxide is 20 % by weight) and be mixed to form liquid mixture as the acetonitrile (not comprising the acetonitrile in oxidizing agent solution) of solvent, liquid mixture to be sent in fixed-bed reactor and to flow through beds.Wherein, the mol ratio of 1-butylene and tertbutyl peroxide is 1:1, and the mol ratio of 1-butylene and solvent acetonitrile (not comprising the acetonitrile in oxidizing agent solution) is 1:30, and the weight hourly space velocity of 1-butylene is 2h
-1.The initial charge temperature of liquid mixture is 45 DEG C, and by the heater strip be arranged in beds, beds being heated to temperature is 45 DEG C, in reaction process, and the heating condition of heater strip remains unchanged.Original pressure in fixed-bed reactor is controlled as 1.2MPa.
The composition of the reaction mixture exported from reactor is monitored continuously, at first time butylene oxide ring selectivity S in reaction process
twith initial (reaction proceeds to 2 little sampling and measuring constantly) butylene oxide ring selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0during <0.9 (that is, satisfy condition 1 time), improve the feeding temperature of liquid mixture until butylene oxide ring selectivity S ' and initial epoxy butane selectivity S with the amplitude of 0.02-2 DEG C/day
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving the feeding temperature of liquid mixture and the temperature (that is, set-up procedure A) after being remained rising, to satisfy condition for the 2-4 time 1 time, improve the quality of tertbutyl peroxide in liquid mixture with the amplitude in 0.02-0.1%/sky (to be realized by the concentration improving tertbutyl peroxide in oxidizing agent solution, the consumption of corresponding reduction oxidizing agent solution simultaneously, to keep the mol ratio of 1-butylene and tertbutyl peroxide constant) until satisfy condition 2 time, stop improving the quality of tertbutyl peroxide and numerical value after remaining raising (namely, set-up procedure B), the rest may be inferred (namely, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, wherein, three set-up procedure B are carried out) between adjacent twice set-up procedure A.
Carry out the reaction of 720 hours, at the end of reaction, the feeding temperature of liquid mixture is 52 DEG C, and in oxidizing agent solution, the quality of tertbutyl peroxide is 70 % by weight.The butylene oxide ring selectivity that the reaction mixture being proceeded to 2 hours by reaction and obtained for 720 hours is determined is listed in table 3.
Table 3
Claims (14)
1. an olefin oxidation method, the method comprises makes a kind of liquid mixture and HTS contact reacts in the reactor, described liquid mixture contains alkene, at least one oxygenant and optional at least one solvent, wherein, the method also comprises the set-up procedure of at least carrying out once, satisfy condition 1 time carry out described set-up procedure, to improve desirable oxidation selectivity of product until satisfy condition 2 time stop described set-up procedure
Desirable oxidation selectivity of product S under condition 1, sometime t
twith initial target oxidation products selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S
0ratio S '/S
0be 0.9≤S '/S
0≤ 1;
Described 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 temperature improving described liquid mixture;
Set-up procedure B: the quality improving oxygenant in described liquid mixture.
2. method according to claim 1, wherein, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, and carry out set-up procedure A at least one times between adjacent twice set-up procedure B, or carry out set-up procedure B at least one times between adjacent twice set-up procedure A.
3. method according to claim 1 and 2, wherein, in condition 1, S
t/ S
0<0.9.
4. method according to claim 1, wherein, improves the temperature of liquid mixture with the amplitude of 0.01-5 DEG C/day; And/or
The quality of oxygenant in described liquid mixture is improved with the amplitude in 0.02-5%/sky.
5. method according to claim 1, wherein, described HTS is seated in the beds of fixed-bed reactor, described beds comprises the first beds and the second beds, described liquid mixture flows through described first beds and described second beds successively, and the HTS that the HTS of described first beds filling and described second beds load is identical or different.
6. method according to claim 5, wherein, the HTS of described first beds filling is hollow HTS, the crystal grain of described hollow HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm; And
The HTS of described second beds filling is titanium-silicon molecular sieve TS-1.
7. the method according to claim 5 or 6, wherein, the weight ratio of the HTS that the HTS of described first beds filling and described second beds load is 0.1-20:1, is preferably 2-10:1.
8. according to the method in claim 5-7 described in any one, wherein, described liquid mixture flows through the superfacial velocity of the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, v
1< v
2; Preferably, v
2/ v
1=1.5-15; More preferably, v
2/ v
1=2-5.
9. according to the method in claim 5-8 described in any one, wherein, the residence time of described liquid mixture in described beds is T, and the residence time in described first beds is T
1, T
1/ T=0.2-0.95; Preferably, T
1/ T=0.5-0.85.
10. according to the method in claim 1,2 and 4-6 described in any one, wherein, the temperature of described liquid mixture is in the scope of 0-120 DEG C.
11. according to the method in claim 1,2 and 4-6 described in any one, and wherein, the mol ratio of described oxygenant and alkene is in the scope of 0.1-10:1.
12. according to the method in claim 1,2 and 4-6 described in any one, and described alkene is propylene and/or butylene.
13. according to the method in claim 1,2 and 4-6 described in any one, and described oxygenant is superoxide.
14. methods according to claim 13, wherein, described oxygenant is selected from hydrogen peroxide, organo-peroxide and peracid.
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