CN105481798A - Method for oxidating alkene - Google Patents
Method for oxidating alkene Download PDFInfo
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- CN105481798A CN105481798A CN201410514050.1A CN201410514050A CN105481798A CN 105481798 A CN105481798 A CN 105481798A CN 201410514050 A CN201410514050 A CN 201410514050A CN 105481798 A CN105481798 A CN 105481798A
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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 a method for oxidating alkene. The method comprises the step of enabling a liquid mixture to flow through a catalyst bed layer in a fixed bed reactor under the condition of oxidation reaction so as to be in contact with titanium silicalite molecular sieves filled in the catalyst bed layer, wherein the liquid mixture contains alkene, at least one oxidant and optional at least one solvent; and when the selectivity of a target oxidation product is lower than an expected value, the method further comprises the step of increasing the interior pressure of the fixed bed reactor or increasing the interior pressure of the fixed bed reactor and increasing the mass of the oxidant in the liquid mixture. According to the method, the selectivity of the target oxidation product can be always maintained at a high level high level, on one hand, the frequent adjustment on operating conditions according to the composition of a reaction mixture in a subsequent separation and purification process is avoided; and on the other hand, the single-pass service lives of the titanium silicalite molecular sieves as a catalyst are effectively prolonged, and the regeneration frequency of the catalyst is lowered.
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 of catalyzer can reduce, namely catalyzer there will be deactivation phenomenom in operation process, causes the desirable oxidation selectivity of product in the reaction mixture obtained to decline.
For decaying catalyst, 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 Fluctuation of catalyzer is comparatively large, needs could stablize for a long time, causes obtaining stable desirable oxidation selectivity of product.In addition, when the catalyzer of regeneration puts into operation again, also need to combine the smooth running that operations such as improving temperature of reaction carrys out realization response, but these operate the inactivation of often accelerator activator.
Therefore, using HTS as in the technique of catalyzer, no matter be when HTS inactivation, or when again putting into operation through the HTS of regeneration, all may there is the problem of target product selectivity instability in the reaction mixture obtained, cause the composition of mixture to change.Because the composition of the mixture be obtained by reacting is unstable, follow-up separation and purification process also needs corresponding adjustment, improves the complicacy of operation on the one hand, also has a negative impact to the stability of quality product on the other hand.
To sum up, using HTS as in the technique of catalyzer, need badly and solve following problem: occur deactivation phenomenom at catalyzer, when causing target product selectivity to reduce, how target product selectivity is maintained higher level, thus the one way work-ing life of extending catalyst, reduce regeneration frequency.
Summary of the invention
The object of the present invention is to provide a kind of method of olefin oxide, adopt the method olefin oxide, desirable oxidation selectivity of product can be maintained higher level for a long time, thus the one way work-ing life of extending catalyst, reduce catalyst regeneration frequency.
The invention provides a kind of olefin oxidation method, under the method is included in oxidation reaction condition, in fixed-bed reactor, a kind of liquid mixture is made to flow through beds, to contact with the HTS be seated in beds, 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: improve the pressure in fixed-bed reactor;
Set-up procedure B: the quality improving the 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 flowed out by fixed-bed reactor is determined is lower than desired value, carry out set-up procedure, namely improve pressure or the pressure improved in reactor in reactor and improve oxygenant quality in liquid feeding, 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 frequently 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.
Embodiment
The invention provides a kind of olefin oxidation method, under the method is included in oxidation reaction condition, in fixed-bed reactor, a kind of liquid mixture is made to flow through beds, to contact with the HTS be seated in beds, described liquid mixture contains alkene, at least one oxygenant and optional at least one solvent.
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, 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.
The consumption of described oxygenant can be selected according to the amount of alkene.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 0.5-3:1, preferred in the scope of 1-2:1 further.
According to method of the present invention, described liquid mixture can contain solvent, also can not contain solvent, preferably also containing 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.Preferably, 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 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 3-40:1, more preferably 5-20:1.
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).
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.
According to method of the present invention, 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.
Preferably, described HTS is hollow HTS, can obtain the catalyzer one way work-ing life extended further like this, can also obtain better catalytic effect simultaneously, obtain higher target product selectivity.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, described HTS is seated in the beds of fixed-bed reactor, thus contacts with described liquid mixture.The quantity of described beds can be one or more.When the quantity of beds is multiple, the different zones of fixed-bed reactor can be positioned at, also can be arranged in multiple fixed-bed reactor.
In one embodiment of the invention, described beds contains the first beds and the second beds, with the flow direction of described liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, namely described liquid mixture first flows through the first beds, then flows through the 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, the one way work-ing life of HTS can not only be extended so further, and selectivity of product can also be improved 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, 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.D
1/ D
2be preferably more than 1.5, be more preferably more than 2.D
1/ D
2be preferably less than 15, be more preferably less than 10, more preferably less than 5.Particularly, D
1/ D
2can be 1.5-15, be preferably 2-5.
According to method of the present invention, 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 0.8.Further preferably, T
1/ T=0.5-0.85.
According to method of the present invention, fresh 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: supplement in alkene, oxygenant and optional solvent between the first beds and the second beds, between the first beds and/or between the second beds one or more.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.
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.
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.Usually, the median size of described shaping HTS can be 4-5000 micron, is preferably 5-2000 micron, as 40-1000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
The consumption of described HTS can be selected according to the concrete treatment capacity of device.Usually, the weight hourly space velocity of described alkene can be 0.1-20h
-1, be preferably 1-10h
-1.Described weight hourly space velocity with the total amount of HTS for benchmark.
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, also comprise 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: improve the pressure in fixed-bed reactor;
Set-up procedure B: the quality improving the oxygenant in described liquid mixture.
According to method of the present invention, satisfy condition 2 time, stop the pressure improving in fixed-bed reactor also pressure to be remained the numerical value 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 a higher level all the 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 pressure or the pressure improved in fixed-bed reactor in fixed-bed reactor and improve the quality of the oxygenant in described liquid mixture until satisfy condition 2, but in set-up procedure A, preferably improve pressure with the amplitude of 0.01-1MPa/ days; 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 so on the one hand, reaction can also be enable to carry out more reposefully on the other hand.More preferably, in described set-up procedure A, improve pressure with the amplitude of 0.02-0.5MPa/ days.In the present invention, " amplitude " refers to the step-length between adjacent two numerical value.
According to method of the present invention, the pressure in fixed-bed reactor can be improved by the method controlling back pressure apparatus pressure.When improving the pressure in fixed-bed reactor, all the other operational conditionss of fixed-bed reactor, such as: temperature, can remain unchanged, also correspondingly can adjust, preferably remain unchanged.The raising degree of the pressure in fixed-bed reactor can be determined according to the specific requirement of reactor.Preferably, the top pressure in fixed-bed reactor is not higher than 5MPa (in gauge pressure).Original pressure in described fixed-bed reactor can be normal pressure (that is, counting 0MPa with gauge pressure) or higher than normal pressure (as counted more than 0.1MPa with gauge pressure).Original pressure in described fixed-bed reactor is preferably not higher than 3MPa.Described original pressure refers to the pressure that reaction starts.In actual production process, pressure when device can be realized steady running is as original pressure.
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 be preferably not higher than 10:1, be more preferably not higher than 5:1, more 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, improve the concentration of oxygenant in oxidizing agent solution gradually, improve the quality of oxygenant in liquid mixture, realize reaction is carried out in the presence of at least one solvent simultaneously.
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, oxidation reaction condition can carry out selectivity according to the oxidation products of expection.Usually, the temperature in beds can be 0-120 DEG C.From the optionally angle improved further for epoxide, the temperature in beds is preferably 20-80 DEG C, is more preferably 30-60 DEG C.
According to method of the present invention, when described beds comprises previously described first beds and the second beds, the temperature of described first beds and the temperature of described beds can be identical or different, can be in separately in the scope of 0-120 DEG C (preferred 20-80 DEG C, more preferably 30-60 DEG C).From further improving desirable oxidation selectivity of product and oxygenant effective rate of utilization, and the angle extending one way work-ing life of HTS is further set out, and preferably the temperature of described first beds is the temperature higher than described second beds.More preferably, the temperature of described first beds is than the temperature height 5-30 DEG C of described second beds, preferred high 10-20 DEG C.
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 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.
According to method of the present invention, effectively can extend the one way work-ing life of the HTS as catalyzer, make device can steady running within the longer time, reduce running cost; Further, method of the present invention, when for olefin oxidation is prepared epoxide, can obtain higher epoxide selectivities.
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, if not otherwise specified, agents useful for same is commercially available analytical reagent, and pressure is gauge pressure, and HTS used is fresh titanium si molecular sieves.
In following examples and comparative example, hollow HTS used is prepared according to method disclosed in Chinese patent CN1132699C, and its titanium oxide content is 2.5 % by weight; Titanium-silicon molecular sieve TS-1 used is by JournalofNaturalGasChemistry, 2001, in 10 (4): 295-307 the 296th page of 9-24 capable described by method prepare, its titanium oxide content is 2.5 % by weight; Ti-MCM-41 HTS 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.; Ti-Beta HTS 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, adopt vapor-phase chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant effective rate of utilization, the epoxide selectivities as desirable oxidation product and the acetaldehyde selectivity as by product on this basis respectively:
Oxygenant effective rate of utilization=(mole number of the oxygenant of mole number/reaction consumption of the epoxide that reaction generates) × 100%;
Epoxide selectivities=(mole number of the alkene of mole number/reaction consumption of the epoxide that reaction generates) × 100%;
Acetaldehyde selectivity=(mole number of the alkene of mole number/reaction consumption of the acetaldehyde that reaction generates) × 1000000.
Embodiment 1-22 is for illustration of method of the present invention.
Embodiment 1
By catalyzer, (volume average particle size is the spherical catalyst of 700 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 0.74g/cm
3) be seated in fixed-bed reactor, form beds, wherein, the quantity of beds is 1 layer.
To send into from the bottom of fixed-bed reactor after the mixing of propylene, the hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) as oxygenant and the acetone as solvent and flow through beds.Wherein, the mol ratio of propylene and hydrogen peroxide is 1:0.5, and the mol ratio of propylene and solvent acetone is 1:5, and the weight hourly space velocity of propylene is 2.2h
-1.Temperature in beds is 35 DEG C, in reaction process controls the original pressure in fixed-bed reactor for 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≤C
t/ C
0during <0.9 (that is, satisfy condition 1 time), raise pressure in fixed-bed reactor until propylene oxide selectivity S ' and initial epoxy propane selectivity S with the amplitude of 0.02-0.5MPa/ days
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop boosting and carrying out pressurize.
Carry out the reaction of 740 hours, the pressure at the end of reaction in fixed-bed reactor is 4.4MPa.Oxygenant effective rate of utilization, propylene oxide selectivity and acetaldehyde selectivity that the reaction mixture being proceeded to 0.5 hour by reaction and obtained for 740 hours is determined are listed respectively in Table 1.
Comparative example 1
Adopt the method propylene oxide identical with embodiment 1, unlike, do not change the pressure in fixed-bed reactor in reaction process.
The result of reacting 0.5 hour and 360 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, raise the pressure in fixed-bed reactor with the amplitude of 0.02-0.5MPa/ days until satisfy condition 2 time, stop boosting and carrying out pressurize; To satisfy condition for the 2nd time 1 time, the quality improving hydrogen peroxide in liquid mixture with the amplitude in 0.02-5%/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, raise pressure in fixed-bed reactor until satisfy condition 2 with the amplitude of 0.02-0.5MPa/ days; Even-times satisfy condition 1 time, improve the quality of hydrogen peroxide in liquid mixture until satisfy condition 2 with the amplitude in 0.02-5%/sky).
Carry out the reaction of 820 hours, the pressure at the end of reaction in fixed-bed reactor is 3.1MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 58 % by weight.The result of reacting 0.5 hour and 820 hours is listed in Table 1.
Embodiment 3
Adopt the method propylene oxide identical with embodiment 2, unlike, (namely the hollow HTS of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer replaces, shaping hollow HTS, the content of catalyzer hollow core HTS is 80 % by weight, the content of silicon oxide is 20 % by weight, and the density of catalyzer is 0.69g/cm
3).
Carry out the reaction of 850 hours, the pressure at the end of reaction in fixed-bed reactor is 2.8MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 59 % by weight.The result of reacting 0.5 hour and 850 hours is listed in Table 1.
Embodiment 4
Adopt the method propylene oxide identical with embodiment 2, unlike, (namely the HTS Ti-MCM-41 of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer replaces, shaping HTS Ti-MCM-41, in catalyzer, the content of HTS Ti-MCM-41 is 80 % by weight, the content of silicon oxide is 20 % by weight, and the density of catalyzer is 0.62g/cm
3).
Carry out the reaction of 780 hours, the pressure at the end of reaction in fixed-bed reactor is 3.0MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 60 % 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, (namely the HTS Ti-Beta of the titanium-silicon molecular sieve TS-1 equivalent in catalyzer replaces, shaping HTS Ti-Beta, in catalyzer, the content of HTS Ti-Beta is 80 % by weight, the content of silicon oxide is 20 % by weight, and the density of catalyzer is 0.77g/cm
3).
Carry out the reaction of 800 hours, the pressure at the end of reaction in fixed-bed reactor is 3.2MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 59 % by weight.The result of reacting 0.5 hour and 800 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, the pressure at the end of reaction in fixed-bed reactor is 2.6MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 56 % 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, (that is, liquid mixture is first by shaping titanium-silicon molecular sieve TS-1 for shaping hollow HTS of recharging, again by 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, the pressure at the end of reaction in fixed-bed reactor is 2.9MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 58 % 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, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:1.
Carry out the reaction of 960 hours, the pressure at the end of reaction in fixed-bed reactor is 2.8MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 59 % by weight.The result of reacting 0.5 hour and 960 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, the weight ratio of shaping hollow HTS and shaping titanium-silicon molecular sieve TS-1 is 1:2.
Carry out the reaction of 900 hours, the pressure at the end of reaction in fixed-bed reactor is 2.9MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 60 % by weight.The result of reacting 0.5 hour and 900 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, the pressure at the end of reaction in fixed-bed reactor is 2.5MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 57 % 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 980 hours, the pressure at the end of reaction in fixed-bed reactor is 2.7MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 58 % by weight.The result of reacting 0.5 hour and 980 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 920 hours, the pressure at the end of reaction in fixed-bed reactor is 2.8MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 59 % by weight.The result of reacting 0.5 hour and 920 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 950 hours, the pressure at the end of reaction in fixed-bed reactor is 2.9MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 56 % by weight.The result of reacting 0.5 hour and 950 hours is listed in Table 1.
Table 1
Embodiment 1 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, the mass combination improving oxygenant in reaction pressure and raising liquid mixture is used, the one way work-ing life of HTS can be extended further.
Embodiment 14
In reducing fixed-bed reactor, loading shaping hollow HTS, (volume average particle size is the spherical catalyst of 200 μm, and density is 0.71g/cm
3wherein, the content of hollow HTS is 85 % by weight, the content of silicon oxide is 15 % by weight), form beds, wherein, reducing fixed-bed reactor have the beds for loading HTS of two different inner diameters, be 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, the weight ratio of the shaping hollow HTS of loading in the shaping hollow HTS of loading 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 3:1.
Send into by propylene, hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) from the bottom of fixed-bed reactor as the liquid mixture of the formation of methanol of solvent, successively flow through the first beds and the second beds.Wherein, the mol ratio of propylene and hydrogen peroxide is 1:0.6, and the mol ratio of propylene and methyl alcohol is 1:20, and the weight hourly space velocity of propylene is 2.5h
-1.First beds and the second reaction bed temperature are 40 DEG C, and the original pressure in fixed-bed reactor controls as 0.2MPa.
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≤C
t/ C
0during <0.9 (that is, satisfy condition 1 time), raise pressure in fixed-bed reactor until propylene oxide selectivity S ' and initial epoxy propane selectivity S with the amplitude of 0.02-0.5MPa/ days
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop boosting and carrying out pressurize.
Carry out the reaction of 1100 hours, the pressure at the end of reaction in fixed-bed reactor is 1.8MPa.React the oxygenant effective rate of utilization that obtains for 2 hours and 1100 hours and propylene oxide selectivity is listed in table 2.
Comparative example 2
Adopt the method propylene oxide identical with embodiment 14, unlike, the pressure in reaction process not in altering reactor.
The result of reacting 2 hours and 400 hours is listed in table 2.
Embodiment 15
Adopt the method propylene oxide identical with embodiment 14, unlike, the temperature of the first beds controls to be 40 DEG C, and the temperature of the second beds controls to be 20 DEG C.
Carry out the reaction of 1150 hours, the pressure at the end of reaction in fixed-bed reactor is 1.6MPa.The result of reacting 2 hours and obtain for 1150 hours is listed in table 2.
Embodiment 16
Adopt the method propylene oxide identical with embodiment 14, unlike, in reaction process, to satisfy condition for the 1st time 1 time, the quality improving hydrogen peroxide in liquid mixture with the amplitude in 0.02-5%/sky (is realized by the concentration improving hydrogen peroxide in hydrogen peroxide, hydrogen peroxide consumption remains unchanged) until satisfy condition 2 time, stop improving the quality of hydrogen peroxide in liquid mixture and the numerical value (that is, set-up procedure B) after remaining rising; Satisfy condition the 2nd and 3 times 1 time, raise the pressure in fixed-bed reactor with the amplitude of 0.02-0.5MPa/ days until satisfy condition 2 time, stop boosting and carrying out pressurize (namely, set-up procedure A), 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 1200 hours, the pressure at the end of reaction in fixed-bed reactor is 1.5MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 39 % by weight.The result of reacting 2 hours and obtain for 1200 hours is listed in table 2.
Embodiment 17
Adopt the method propylene oxide identical with embodiment 16, unlike, the temperature of the first beds controls to be 40 DEG C, and the temperature of the second beds controls to be 30 DEG C.
Carry out the reaction of 1260 hours, the pressure at the end of reaction in fixed-bed reactor is 1.6MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 38 % by weight.The result of reacting 0.5 hour and 1260 hours is listed in table 2.
Embodiment 18
Adopt the method propylene oxide identical with embodiment 17, unlike, (volume average particle size is the spherical catalyst of 200 μm to the shaping titanium-silicon molecular sieve TS-1 of the shaping hollow HTS equivalent in the second beds, and density is 0.75g/cm
3, wherein, the content of titanium-silicon molecular sieve TS-1 is 85 % by weight, and the content of silicon oxide is 15 % by weight) replace.
Carry out the reaction of 1500 hours, the pressure at the end of reaction in fixed-bed reactor is 1.4MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 35 % by weight.The result of reacting 2 hours and 1500 hours is listed in table 2.
Embodiment 19
Adopt the method propylene oxide identical with embodiment 18, unlike, under the condition that the loadings of the first beds and the second beds is constant, improve the internal diameter of the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 1:1.
Carry out the reaction of 1300 hours, the pressure at the end of reaction in fixed-bed reactor is 1.6MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 37 % by weight.The result of reacting 2 hours and 1300 hours is listed in table 2.
Embodiment 20
Adopt the method propylene oxide identical with embodiment 18, unlike, under the condition that the loadings of the first beds and the second beds is constant, improve the internal diameter of the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 1:2.
Carry out the reaction of 1200 hours, the pressure at the end of reaction in fixed-bed reactor is 2.1MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 41 % by weight.The result of reacting 2 hours and 1200 hours is listed in table 2.
Embodiment 21
The present embodiment uses following two kinds of catalyzer:
Shaping hollow HTS: volume average particle size is the spherical catalyst of 600 μm, density is 0.68g/cm
3, wherein, the content of hollow HTS is 90 % by weight, and the content of silicon oxide is 10 % by weight;
Shaping titanium-silicon molecular sieve TS-1: volume average particle size is the spherical catalyst of 600 μm, density is 0.72g/cm
3, wherein, the content of titanium-silicon molecular sieve TS-1 is 90 % by weight, and the content of silicon oxide is 10 % by weight.
React in reducing fixed-bed reactor, wherein, reducing fixed-bed reactor 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, shaping hollow HTS is loaded in the first beds, titanium-silicon molecular sieve TS-1 is loaded in the second beds, the weight ratio of the shaping titanium-silicon molecular sieve TS-1 loaded in the shaping hollow HTS of loading in the first beds and the second beds is 6:1, the ratio of the internal diameter of the first beds and the internal diameter of the second beds is 4:1.
Propylene, hydrogen peroxide (providing using the hydrogen peroxide form of 20 % by weight) are sent into from the bottom of the fixed-bed reactor being positioned at upstream after the methanol mixed of solvent and flow through the first beds, the liquid mixture of output then to enter in next fixed-bed reactor and flows through the second beds.Wherein, the mol ratio of propylene and hydrogen peroxide is 1:1, and the mol ratio of propylene and methyl alcohol is 1:8, and the weight hourly space velocity of propylene is 4h
-1.The temperature of the first beds controls to be 45 DEG C, and the temperature of the second beds controls to be 30 DEG C, is controlled to be 1.2MPa by the original pressure in fixed-bed reactor in reaction process.
Monitor the composition of the reaction mixture exported from reactor in reaction process continuously, to satisfy condition for the 1st time 1 time (that is, at propylene oxide selectivity S
twith initial (reaction proceeds to 2 little sampling and measuring constantly) propylene oxide selectivity S
0ratio S
t/ S
0be 0.85≤C
t/ C
0during <0.9), with the pressure in the amplitude of 0.02-0.5MPa/ days rising fixed-bed reactor until propylene oxide selectivity S ' and initial epoxy propane selectivity S
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop boosting and carrying out pressurize (that is, set-up procedure A); Satisfy condition the 2nd and 3 times 1 time, the quality improving hydrogen peroxide in liquid mixture with the amplitude in 0.02-5%/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 numerical value after remaining rising (namely, set-up procedure B), the rest may be inferred (that is, between twice set-up procedure A, carrying out twice set-up procedure B).
Carry out the reaction of 1500 hours, the pressure at the end of reaction in fixed-bed reactor is 1.8MPa, and in hydrogen peroxide, the concentration of hydrogen peroxide is 55 % by weight.The result of reacting 2 hours and obtain for 1500 hours is listed in table 2.
Table 2
Embodiment 18-20 is compared and can find out, by catalyzer separately filling, and 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.
Embodiment 22
The fixed-bed reactor that the present embodiment adopts are similar to embodiment 14.
(density is 0.71g/cm to the catalyzer loaded in first beds to be volume average particle size the be spherical shaping hollow HTS of 300 μm
3), wherein, the content of hollow HTS is 75 % by weight, and the content of silicon oxide is 25 % by weight; (density is 0.76g/cm to the catalyzer loaded in second beds to be volume average particle size the be spherical shaping titanium-silicon molecular sieve TS-1 of 300 μm
3), wherein, the content of titanium-silicon molecular sieve TS-1 is 75 % by weight, and the content of silicon oxide is 25 % by weight.
The weight ratio of the shaping titanium-silicon molecular sieve TS-1 loaded in the shaping hollow HTS of loading in the first beds and the second beds is 8:1, and the ratio of the internal diameter of the first beds and the second beds is 5:1.
Using by n-butene, (be hybridly prepared into oxidizing agent solution with acetone as the tertbutyl peroxide of oxygenant, in oxidizing agent solution, the concentration of tertbutyl peroxide is 35 % by weight) and send into from the bottom of fixed-bed reactor as the liquid mixture that the acetone of solvent is formed, flow through the first beds and the second beds successively.Wherein, the mol ratio of n-butene and tertbutyl peroxide is 1:0.7, and the mol ratio of n-butene and solvent acetone (not comprising the acetone in oxidizing agent solution) is 1:8, and the weight hourly space velocity of n-butene is 2.5h
-1.Temperature in first beds is controlled to be 60 DEG C, the temperature in the second beds is controlled to be 45 DEG C.Original pressure in fixed-bed reactor is controlled as 1.2MPa.
Monitor the composition of the reaction mixture exported from reactor in reaction process continuously, to satisfy condition for the 1st time 1 time (that is, at butylene oxide ring selectivity S
twith initial (reaction proceeds to 2 little sampling and measuring constantly) butylene oxide ring selectivity S
0ratio S
t/ S
0be 0.85≤C
t/ C
0during <0.9), the quality (realized by the concentration improving tertbutyl peroxide in oxidizing agent solution, the consumption of maintenance oxidizing agent solution is constant) of tertbutyl peroxide in liquid mixture is improved until butylene oxide ring selectivity S ' and initial epoxy butane selectivity S with the amplitude in 0.02-5%/sky
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving the quality of tertbutyl peroxide in liquid mixture and the numerical value (that is, set-up procedure B) after remaining rising; To satisfy condition for the 2-4 time 1 time, raise the pressure in fixed-bed reactor with the amplitude of 0.02-0.5MPa/ days until satisfy condition 2 time, stop boosting and carrying out pressurize (namely, set-up procedure A), 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, three times set-up procedure A are carried out).
Carry out the reaction of 1500 hours, the pressure at the end of reaction in fixed-bed reactor is 2.8MPa, and in oxidizing agent solution, the concentration of tertbutyl peroxide is 44 % by weight.The result of reacting 2 hours and 1500 hours is listed in table 3.
Table 3
Claims (17)
1. an olefin oxidation method, under the method is included in oxidation reaction condition, in fixed-bed reactor, a kind of liquid mixture is made to flow through beds, to contact with the HTS be seated in beds, 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: improve the pressure in fixed-bed reactor;
Set-up procedure B: the quality improving the 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, satisfy condition 1 time, carry out set-up procedure A or set-up procedure B, and at least carry out a set-up procedure B 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, in gauge pressure, the pressure in described fixed-bed reactor is in the scope of 0-5MPa;
The mol ratio of described oxygenant and alkene is in the scope of 0.1-10:1.
5. according to the method in claim 1,2 and 4 described in any one, wherein, improve pressure with the amplitude of 0.01-1MPa/ days; And/or
The quality of oxygenant in described oxidizing agent solution is improved with the amplitude in 0.02-5%/sky.
6. method according to claim 1, wherein, described beds comprises the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, and the HTS that the HTS of described first beds filling and described second beds load is identical or different.
7. method according to claim 6, 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.
8. the method according to claim 6 or 7, 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.
9. according to the method in claim 6-8 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.
10. according to the method in claim 6-9 described in any one, wherein, the residence time of described liquid mixture in the first beds is T
1, the total residence time in beds is T, T
1/ T=0.2-0.95; Preferably, T
1/ T=0.5-0.85.
11. according to the method in claim 6-10 described in any one, and wherein, the temperature of described first beds is higher than the temperature of described second beds.
12. methods according to claim 11, wherein, the temperature of described first beds is than the temperature height 5-30 DEG C of described second beds.
13. according to the method in claim 1,2,4 and 6-12 described in any one, and wherein, the temperature in described beds is 0-120 DEG C.
14. according to the method in claim 1,2,4,6 and 7 described in any one, and wherein, described oxygenant is superoxide.
15. methods according to claim 14, wherein, described oxygenant is selected from hydrogen peroxide, organo-peroxide and peracid.
16. according to the method in claim 1,2,4,6 and 7 described in any one, and wherein, described alkene is propylene and/or butylene.
17. according to the method in claim 1,2,4,6 and 7 described in any one, and wherein, with the total amount of the HTS in beds for benchmark, the weight hourly space velocity of described alkene is 0.1-20h
-1.
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