CN104803953A - Olefin epoxidation method - Google Patents
Olefin epoxidation method Download PDFInfo
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- CN104803953A CN104803953A CN201410041272.6A CN201410041272A CN104803953A CN 104803953 A CN104803953 A CN 104803953A CN 201410041272 A CN201410041272 A CN 201410041272A CN 104803953 A CN104803953 A CN 104803953A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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Abstract
An olefin epoxidation method is characterized in that olefin and an oxidant contact and react with a catalyst on a fixed bed under olefin oxidation reaction conditions, and the feeding air speed of a solvent is improved according to a rate of 0.01-2.0h<-1>/d when an index (a) the conversion rate of the oxidant in reaction process reduces to 90% and/or an index (b) the selectivity of a target product olefin oxide reduces to 92% in order to maintain the feeding air speed of the solvent when an index (c) the conversion rate of the oxidant rises to 94% and/or an index (d) the selectivity of the target product olefin oxide rises to 94%. The method maintains the conversion rate of the oxidant and the selectivity of olefin oxide in a high range in the reaction contact process, and delays the inactivation of the catalyst in order to prolong the entire life of the catalyst and prolong the total operation time.
Description
Technical field
The present invention relates to a kind of olefin epoxidation method.
Background technology
Olefin oxide is the important oxygen-containing organic compound of a class, and as propylene oxide (propylene oxide is called for short PO), be also called propylene oxide, be a kind of important basic organic chemical industry raw material, in acryloyl derivative, output is only second to polypropylene.The maximum purposes of PO 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 tensio-active agent, the production of oil field demulsifier etc.
Along with the widespread use of polyurethane material etc., the demand of propylene oxide is rising year by year.At present, the technique of industrial production propylene oxide also exists drawback, does not especially meet the requirement of green chemistry chemical technology.Therefore, people are in the urgent need to exploitation i.e. economy and but also environment amenable production method.
The appearance of HTS (as US4410501), for the oxidation etc. of alkene epoxidation, phenol hydroxylation, keto-alcohol opens up a new way, particularly in alkene epoxidation, achieves good catalytic oxidation effect.Take hydrogen peroxide as oxygenant, in the methyl alcohol reaction system that is solvent, HTS has higher catalytic activity to propylene, and at present, Dow/BASF and Degussa/Uhde pushes this technique to industrialization.
But the common problem existed is that device operates after for some time, and the activity and selectivity of catalyzer can reduce, and namely catalyzer deactivation phenomenom can occur in operation process.The mode mainly solved at present adopts in-situ regeneration and ex-situ regeneration two kinds of modes to make renewing catalyst activity.Wherein, in-situ regeneration is mainly for the situation that level of deactivation is lighter, and general solvent and/or the oxygenant of adopting floods at a certain temperature or rinse certain hour to realize; Ex-situ regeneration is mainly for the situation that level of deactivation is more serious, and the general modes such as roasting that adopt realize.General industrially employing first makes renewing catalyst activity through in-situ regeneration, after in-situ regeneration cannot make catalyst activity recover by the time, then adopts ex-situ regeneration.Such regeneration Problems existing is when reruning after regeneration, when particularly reruning after in-situ regeneration, the activity and selectivity fluctuation of catalyzer is larger, need could stablize for a long time, the smooth operation of realization response will be carried out in conjunction with operations such as improving temperature of reaction simultaneously, but the further accelerator activator inactivation of meeting and reduction object selectivity of product, affect subsequent product refining spearation, be also unfavorable for safety in production like this.
CN101279959A discloses a kind of method of synthesizing epoxypropane, it is characterized in that the low-carbon alcohol of mol ratio 1 ~ 15:0.5 ~ 5:1, propylene, hydrogen peroxide are in the reactor that catalyzer is housed, propylene and hydrogen peroxide initial ring oxidizing reaction obtain propylene oxide, wherein solution ph and temperature of reaction regulate according to hydrogen peroxide transformation efficiency at any time in whole reaction process, hydrogen peroxide transformation efficiency one is reduced to 88.5%, just improves solution ph and temperature of reaction.This invention can single run life-span of extending catalyst by regulator solution pH value and temperature of reaction.But this method is unfavorable for the repeated multiple times regeneration of catalyzer, increase catalyst consumption, and then increase production cost.
Summary of the invention
Namely object of the present invention is to provide a kind of olefin epoxidation method.
The present inventor experimental studies have found that through a large amount of, when oxygenant low conversion rate in epoxidation reaction of olefines operational process in 90% and/or object product olefin oxide selectivity lower than 92% time, the Feed space velocities of solvent is improved with certain amplitude, the selectivity of the transformation efficiency and object product olefin oxide that can maintain oxygenant is in higher level, and then extend alkene epoxidation parallel-adder settle-out time, surprisingly the effective rate of utilization of oxygenant is improved.Based on this, complete the present invention.
Olefin epoxidation method provided by the invention, under olefin hydrocarbon oxidation reaction condition, alkene and oxygenant is made to carry out contact reacts with catalyzer on a fixed bed, the transformation efficiency that it is characterized in that comprising oxygenant in index (a) reaction process reduces, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.01 ~ 2.0h
-1the amplitude of/d improves the Feed space velocities of solvent, make the transformation efficiency when index (c) oxygenant increase, touch 94% and/or index (d) object product olefin oxide selectivity rising, when touching 94%, the step of the Feed space velocities of maintenance solvent.
Method provided by the invention, the total transformation efficiency of oxygenant and object selectivity of product can be maintained in higher scope in reaction contact process, delay catalyst deactivation simultaneously, total working time is extended, improve the entire life of catalyzer, surprisingly the effective rate of utilization of oxygenant is improved.Process of the present invention is simple and easy to control, is beneficial to suitability for industrialized production and application.
Embodiment
Olefin epoxidation method provided by the invention, under olefin hydrocarbon oxidation reaction condition, alkene and oxygenant is made to carry out contact reacts with catalyzer on a fixed bed, the transformation efficiency that it is characterized in that comprising oxygenant in index (a) reaction process reduces, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.01 ~ 2.0h
-1the amplitude of/d improves the Feed space velocities of solvent, make the transformation efficiency when index (c) oxygenant increase, touch 94% and/or index (d) object product olefin oxide selectivity rising, when touching 94%, the step of the Feed space velocities of maintenance solvent.
In method provided by the invention, These parameters percentage ratio all refers to the form of molecular fraction, and namely index (a) is the transformation efficiency (molecular fraction) of oxygenant in reaction process; The selectivity (molecular fraction) of index (b) object product olefin oxide; The transformation efficiency (molecular fraction) of index (c) oxygenant; The selectivity (molecular fraction) of index (d) object product olefin oxide.
In said method, said alkene is the alkene being not more than 12 carbon atoms, and preferred carbonatoms is the alkene of 2 ~ 6, can be monoolefine or polyene hydrocarbon, preferred monoolefine, more preferably propylene and butylene.
In said method, the specific examples of oxygenant 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.Be normally that the form of the aqueous hydrogen peroxide solution of 5 ~ 70% adds in reaction system with mass percentage concentration, the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30%, 55% and 70% etc.
In said method, in order to improve the efficiency of reaction, solvent is introduced in reaction system, solvent used comprises ketone, alcohols, nitrile, such as be selected from one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile, vinyl cyanide, wherein particular methanol, acetone or the trimethyl carbinol.Wherein, said solvent selected from methanol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone, particular methanol, the trimethyl carbinol or acetone, more preferably solvent is methyl alcohol.
In said method, be preferred embodiment the transformation efficiency changing into oxygenant in reaction process when index (a) reduce, touch 92% and/or when the selectivity that index (b) changes into object product olefin oxide reduce, touch 94% time, the amplitude of Feed space velocities of raising solvent is 0.02 ~ 1.0h
-1/ d, makes the transformation efficiency changing into oxygenant when index (c) rise, touches 95% and/or index (d) selectivity of changing into object product olefin oxide rises, when touching 95%, keep the Feed space velocities of solvent.
The present inventor is also surprised to find that, by adopting the Feed space velocities improving solvent to combine with the measure of the mass concentration improving oxygenant in raw material, when preferably mutually hocketing, obtains better technique effect.
Therefore, in preferred embodiment of the present invention, comprise the steps: (1) when the transformation efficiency of oxygenant in index (a) reaction process reduce, touch 90% and/or index (b) object product olefin oxide selectivity reduce, touch 92% time, with 0.01 ~ 2.0h
-1the amplitude of/d improves the Feed space velocities of solvent, makes the transformation efficiency of index (c) oxygenant increase, touches 94% and/or the selectivity of index (d) object product olefin oxide rises, when touching 94%, keep the Feed space velocities of solvent; (2) when the transformation efficiency of oxygenant in index (a) reaction process again reduce, touch 90% and/or the selectivity of index (b) object product olefin oxide again reduce, touch 92% time, the mass concentration of oxygenant in raw material is improved with the amplitude of 0.02 ~ 5%/d, make the transformation efficiency when index (c) oxygenant again increase, touch 94% and/or the selectivity of index (d) object product olefin oxide rises again, when touching 94%, keep the mass concentration of oxygenant.Hocket in above-mentioned steps (1) and (2), the measure namely adjusting the mass concentration of oxygenant in the Feed space velocities of solvent and raw material hockets, and be more conducive to the performance of catalyst catalytic performance, runtime is longer.
In method provided by the invention, said catalyzer take HTS as active component, and catalyst grain size is preferably 0.5 ~ 20000 micron.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, HTS chemical formula xTiO
2siO
2during expression, x can be 0.0001 ~ 0.04, 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 of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure.More preferably, described HTS is the titanium-silicon molecular sieve TS-1 of MFI structure.From improving the effective rate of utilization of oxygenant and the angle of selectivity of product further, the crystal grain of described HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5 ~ 300 nanometers, and described 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.Herein, the HTS with this structure is called hollow HTS HTS.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.
Of the present invention preferred embodiment in, said catalyzer is at least set to HTS in fixed bed to be active ingredient and to take TS-1 as two portions beds of active ingredient, and make said material first with the catalyst exposure taking HTS as active ingredient, then with take TS-1 as the catalyst exposure of active ingredient.Catalyzer is in active ingredient, and the mass ratio of said HTS and said TS-1 is 0.1 ~ 20:1, preferably 0.2 ~ 10:1.Adopt the mode of dual catalyst bed, at the transformation efficiency of oxidation agent with while the extending catalyst steady running time, be unexpectedly reduce the probability that side reaction occurs, namely improve selectivity of product.
In method provided by the invention, the amount of catalyzer is without particular determination, and satisfied reaction requires, bed is honest and kind can carry out flexible according to reaction needed.And can, according to reaction needed, utilize inert filler such as quartz sand, ceramic ring, potsherd etc. to dilute catalyzer.
In method provided by the invention, the said Feed space velocities improving solvent with certain amplitude, in weight hourly space velocity, the Feed space velocities improving solvent can mention 10h
-1, even can reach 20h
-1above, the present invention does not have particular requirement to this.If but solvent feed air speed is excessive, increase its energy consumption such as separation and circulation, angularly consider from economy, the Feed space velocities of solvent preferably can bring up to 10h
-1.
In preferred embodiment provided by the invention, the wherein said mass concentration improving oxygenant in raw material with certain amplitude, the mass concentration of oxygenant can mention more than 70%, and even can reach 100%, the present invention does not have particular requirement to this.From raw material be easy to get and economy angularly consider, as oxygenant be aqueous hydrogen peroxide solution time, its mass concentration generally can reach 70%.
Method provided by the invention, wherein, said olefin hydrocarbon oxidation reaction condition is temperature 0 ~ 120 DEG C, pressure 0.01 ~ 5MPa, and the mol ratio of alkene and oxygenant is 1 ~ 10:1, and the mol ratio of solvent and alkene is 0 ~ 100:1, and in system, solvent air speed is 0.1 ~ 20h
-1.Preferably, said temperature is 20 ~ 80 DEG C, and pressure is 0.1 ~ 3MPa, and the mol ratio of alkene and oxygenant is 0.2 ~ 5:1, and the mol ratio of solvent and alkene is 0.2 ~ 80:1, and in system, solvent air speed is 0.1 ~ 10h
-1.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and comparative example, agents useful for same is commercially available chemical pure or analytical reagent.
In embodiment and comparative example, HTS (TS-1) used is by prior art Zeolites, and the TS-1 sieve sample that the method described in 1992, Vol.12 943rd ~ 950 pages is prepared, its titanium oxide content is 2.5 % by weight.Hollow HTS HTS is that Hunan Jianchang Petrochemical Co., Ltd produces, and is the Industrial products of HTS described in Chinese patent CN1132699C.By analysis, this HTS is MFI structure, its titanium oxide content is 2.5 % by weight, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, and crystal grain is hollow crystal grain and the radical length of chamber portion is 15 ~ 180 nanometers; This HTS sample at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity recorded under the condition of 1 hour is 78 milligrams/gram.
In embodiment and comparative example, the preparation method of microspherical catalyst used is as follows: under normal pressure and 60 DEG C of conditions, is first joined in the TPAOH aqueous solution by silicoorganic compound tetraethoxy and mixes, and stirs hydrolysis 5h and obtains colloidal solution; Then HTS is added to mix among above-mentioned gained colloidal solution and obtain slurries, and wherein the mass ratio of HTS, silanes, TPAOH and water is 100:25:5:250; After above-mentioned slurries are continued to stir 2h, after conventional mist projection granulating, roasting can obtain the catalyzer (granularity 20 ~ 80 microns) of the present invention's microballoon shape used.
In embodiment and comparative example, olefin hydrocarbon oxidation reaction is all carry out in common micro fixed-bed reactor.
In comparative example and embodiment, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant transformation efficiency, oxygenant effective rate of utilization and olefin oxide selectivity on this basis respectively:
Comparative example 1
This comparative example illustrates epoxidation of propylene situation when not adopting the inventive method.
Be 2:1 by propylene, hydrogen peroxide, solvent acetone and TS-1 microspherical catalyst according to the mol ratio of propylene and hydrogen peroxide, the mol ratio of solvent and propylene is 10:1, and system solvent weight hourly space velocity is 1.5h
-1, react under be 40 DEG C of pressure being 2.0MPa in temperature.The result of reacting 2 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 95%.The result of reacting 240 hours is as follows: hydrogen peroxide conversion 94%; Effective utilization ratio of hydrogen peroxide is 85%; Propylene oxide selectivity is 91%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 83%; Effective utilization ratio of hydrogen peroxide is 81%; Propylene oxide selectivity is 88%.
Embodiment 1
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with comparative example 1, unlike in reaction after 240 hours, with 0.02 ~ 1.0h
-1the amplitude of/d improves the Feed space velocities of solvent, makes the transformation efficiency when oxygenant increase, touches 94% and the selectivity of object product olefin oxide rises, when touching 94%, the Feed space velocities of maintenance solvent, until the Feed space velocities of raising solvent reaches 10h
-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 93%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 93%.
Embodiment 2
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with embodiment 1, when improving the Feed space velocities of solvent, make the transformation efficiency when oxygenant increase, touch 95% or object product olefin oxide selectivity rising, when touching 95%, the Feed space velocities of maintenance solvent.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 97%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 95%.
Embodiment 3
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with embodiment 2, unlike in reaction after 240 hours, 0.02 ~ 1.0h
-1the amplitude of/d improves the Feed space velocities of solvent, the transformation efficiency when oxygenant is made to increase, touch the selectivity rising of 95% and object product olefin oxide, when touching 95%, keep the Feed space velocities of solvent, when in reaction process, the transformation efficiency of oxygenant reduces again, touch 90% and/or the selectivity of object product olefin oxide again reduce, when touching 92%, the mass concentration of oxygenant in raw material is improved with the amplitude in 0.02 ~ 5%/sky, the transformation efficiency when oxygenant is made again to increase, touch 95% and/or the selectivity of object product olefin oxide again rise, when touching 95%, keep the mass concentration of oxygenant, until the Feed space velocities improving solvent reaches 10h
-1and/or the mass concentration of oxygenant reaches 70%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 96%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 95%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 92%; Propylene oxide selectivity is 95%.
Comparative example 2
This comparative example illustrates epoxidation of propylene situation when not adopting the inventive method.
Be 3:1 by propylene, hydrogen peroxide, solvent methanol and HTS microspherical catalyst according to the mol ratio of propylene and hydrogen peroxide, the mol ratio of solvent and propylene is 10:1, and system solvent weight hourly space velocity is 0.5h
-1, react under be 50 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hydrogen peroxide conversion 98%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 97%.The result of reacting 240 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 92%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 91%; Effective utilization ratio of hydrogen peroxide is 86%; Propylene oxide selectivity is 90%.
Embodiment 4
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with comparative example 2, unlike in reaction after 240 hours, 0.02 ~ 1.0h
-1the amplitude of/d improves the Feed space velocities of solvent, makes the transformation efficiency when oxygenant increase, touches 95% and the selectivity of object product olefin oxide rises, when touching 95%, the Feed space velocities of maintenance solvent, until the Feed space velocities of raising solvent reaches 10h
-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 96%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 95%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 94%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 93%.
Embodiment 5
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 4, HTS and TS-1 being 10:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 98%; Effective utilization ratio of hydrogen peroxide is 95%; Propylene oxide selectivity is 98%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 94%; Propylene oxide selectivity is 97%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 92%; Propylene oxide selectivity is 96%.
Embodiment 6
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition, with embodiment 5, unlike making said alkene first contact with TS-1 with oxygenant, then contacts with HTS.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 93%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 91%; Effective utilization ratio of hydrogen peroxide is 87%; Propylene oxide selectivity is 91%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 82%; Effective utilization ratio of hydrogen peroxide is 82%; Propylene oxide selectivity is 85%.
Embodiment 7
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 5, HTS and TS-1 being 15:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 93%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 93%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 91%; Effective utilization ratio of hydrogen peroxide is 84%; Propylene oxide selectivity is 90%.
Embodiment 8
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 5, HTS and TS-1 being 1:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 98%; Effective utilization ratio of hydrogen peroxide is 94%; Propylene oxide selectivity is 97%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 95%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 92%; Propylene oxide selectivity is 95%.
Embodiment 9
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with embodiment 5, unlike in reaction after 240 hours, 0.02 ~ 1.0h
-1the amplitude of/d improves the Feed space velocities of solvent, the transformation efficiency when oxygenant is made to increase, touch the selectivity rising of 95% and object product olefin oxide, when touching 95%, keep the Feed space velocities of solvent, when in reaction process, the transformation efficiency of oxygenant reduces again, touch 90% and/or the selectivity of object product olefin oxide again reduce, when touching 92%, the mass concentration of oxygenant in raw material is improved with the amplitude in 0.02 ~ 5%/sky, the transformation efficiency when oxygenant is made again to increase, touch 95% and/or the selectivity of object product olefin oxide again rise, when touching 95%, keep the mass concentration of oxygenant, until the Feed space velocities improving solvent reaches 10h
-1and/or the mass concentration of oxygenant reaches 70%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 98%; Effective utilization ratio of hydrogen peroxide is 95%; Propylene oxide selectivity is 97%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 95%; Propylene oxide selectivity is 96%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 95%; Propylene oxide selectivity is 95%.
Embodiment 10
The present embodiment illustrates alkene epoxidation situation when adopting the inventive method.
Alkene epoxidation condition, with embodiment 5, substitutes propylene unlike alkene by butylene, and oxygenant replaces hydrogen peroxide by tertbutyl peroxide.The result of reacting 360 hours is as follows: tertbutyl peroxide transformation efficiency 93%; Oxygenant effective rate of utilization is 88%; Butylene oxide ring selectivity is 95%.The result of reacting 720 hours is as follows: tertbutyl peroxide transformation efficiency 92%; Oxygenant effective rate of utilization is 86%; Butylene oxide ring selectivity is 93%.The result of reacting 960 hours is as follows: tertbutyl peroxide transformation efficiency 91%; Oxygenant effective rate of utilization is 83%; Butylene oxide ring selectivity is 90%.
As can be seen from embodiment and comparative example: production method maintenance oxygenant effective rate of utilization of the present invention and object selectivity of product, in higher scope, delay catalyst deactivation, and then make extend total working time, improve the entire life of catalyzer simultaneously.Particularly as can be seen from the contrast of embodiment 4 ~ 9: when catalyzer is at least set to HTS be active ingredient and take TS-1 as two portions beds of active ingredient in fixed bed, and make the first catalyst exposure with taking HTS as active ingredient of said material, (catalyzer is with active ingredient with the catalyst exposure taking TS-1 as active ingredient again, the mass ratio of said HTS and said TS-1 is 0.1 ~ 20:1, preferably 0.2 ~ 10:1) time, better technique effect can be obtained.As can be seen from the contrast of embodiment 2 and 3 and embodiment 5 and 9, the present invention adopts the measure of the mass concentration of oxygenant in the Feed space velocities of adjustment solvent and raw material to hocket, the performance of catalyst catalytic performance is more conducive to compared with the scheme of the Feed space velocities that the present invention adopts separately adjustment solvent, the steady running time is longer, and catalytic performance is better.
Claims (15)
1. an olefin epoxidation method, under olefin hydrocarbon oxidation reaction condition, alkene and oxygenant is made to carry out contact reacts with catalyzer on a fixed bed, the transformation efficiency that it is characterized in that comprising oxygenant in index (a) reaction process reduces, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.01 ~ 2.0h
-1the amplitude of/d improves the Feed space velocities of solvent, make the transformation efficiency when index (c) oxygenant increase, touch 94% and/or index (d) object product olefin oxide selectivity rising, when touching 94%, the step of the Feed space velocities of maintenance solvent.
2., according to the process of claim 1 wherein, said olefin hydrocarbon oxidation reaction condition is temperature 0 ~ 120 DEG C, pressure 0.01 ~ 5MPa, the mol ratio of alkene and oxygenant is 1 ~ 10:1, and the mol ratio of solvent and alkene is 0 ~ 100:1, and in system, solvent air speed is 0.1 ~ 20h
-1.
3. according to the method for claim 2, wherein, said temperature is 20 ~ 80 DEG C, and pressure is 0.1 ~ 3MPa, and the mol ratio of alkene and oxygenant is 0.2 ~ 5:1, and the mol ratio of solvent and alkene is 0.2 ~ 80:1, and in system, solvent air speed is 0.1 ~ 10h
-1.
4. according to the method for one of claims 1 to 3, wherein, said alkene to be carbonatoms be 2 ~ 6 alkene.
5. according to the method for claim 4, wherein, said alkene is propylene or butylene.
6. according to the method for one of claims 1 to 3, wherein, said oxygenant to be mass concentration be 5 ~ 70% aqueous hydrogen peroxide solution.
7. according to the process of claim 1 wherein, said solvent selected from methanol, the trimethyl carbinol or acetone.
8., according to the process of claim 1 wherein, said index (a) is changed into oxygenant transformation efficiency in reaction process and is reduced, touches 92%; The selectivity that said index (b) changes into object product olefin oxide reduces, touches 94%.
9., according to the process of claim 1 wherein, the amplitude of the Feed space velocities of said raising solvent is 0.02 ~ 1.0h
-1/ d.
10., according to the process of claim 1 wherein, the transformation efficiency that said index (c) changes into oxygenant rises, touches 95%; The selectivity that said index (d) changes into object product olefin oxide rises, touches 95%.
11., according to the method for claim 1, is characterized in that, except when in index (a) reaction process the transformation efficiency of oxygenant reduce, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.01 ~ 2.0h
-1the amplitude of/d improves the Feed space velocities of solvent, the transformation efficiency of index (c) oxygenant is made to increase, touch the selectivity rising of 94% and/or index (d) object product olefin oxide, when touching 94%, keep the step (1) of the Feed space velocities of solvent, also comprise step (2): when in index (a) reaction process, the transformation efficiency of oxygenant reduces again, touch 90% and/or the selectivity of index (b) object product olefin oxide again reduce, when touching 92%, the mass concentration of oxygenant in raw material is improved with the amplitude of 0.02 ~ 5%/d, the transformation efficiency when index (c) oxygenant is made again to increase, touch 94% and/or the selectivity of index (d) object product olefin oxide again rise, when touching 94%, keep the mass concentration of oxygenant, hocket in step (1) and (2).
12. according to the method for claim 1 or 11, and wherein, said catalyzer take HTS as active component.
13. according to the method for claim 1 or 11, and wherein, said catalyzer is set to HTS and TS-1 two portions in said fixed bed, and said alkene and oxygenant are first contacted with HTS, then contacts with TS-1.
14. according to the method for claim 13, and wherein, the mass ratio of said HTS and said TS-1 is 1 ~ 20:1.
15. according to the method for claim 14, and wherein, the mass ratio of said HTS and said TS-1 is 2 ~ 10:1.
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