CN110372639A - A kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0 - Google Patents
A kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0 Download PDFInfo
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Abstract
The present invention relates to a kind of methods that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0, in the cumene solution of cumyl hydroperoxide solute, using cumyl hydroperoxide as oxidant, cyclohexene oxide reaction prepares 7-oxa-bicyclo[4.1.0, and catalyst is the Titanium Sieve Molecular Sieve with central hole structure.Catalyst is applied in continuous fixed bed reaction or continuous, and fixed bed reaction condition is that the molar ratio of cyclohexene and cumyl hydroperoxide solute is (2.0~12.0): 1；Cumyl hydroperoxide feed weight air speed is 0.5~2.0h‑1, reaction pressure is 0.2~3.0MPa, and temperature is 40.0~120.0 DEG C.Compared with existing 7-oxa-bicyclo[4.1.0 industrial technology, catalyst is easily recycled, green non-pollution.And the good catalyst activity, 7-oxa-bicyclo[4.1.0 selectivity is high, and catalyst stability is higher, good economy performance, has preferable application effect, can promote the use of in 7-oxa-bicyclo[4.1.0 industrial production.
Description
Technical field
The present invention relates to a kind of methods that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0, more specifically with a kind of titanium silicon point
Son sieve is catalyst, the method that catalysis cyclohexene and cumyl hydroperoxide oxidation reaction prepare 7-oxa-bicyclo[4.1.0.
Background technique
7-oxa-bicyclo[4.1.0 is widely used, is not only important organic synthesis intermediate, can be used for preparing agriculture propargite, oneself
Diacid, nylon66 fiber, epoxy resin coating, rubber accelerator, dyestuff, medicine etc. can also prepare macromolecule regulator, surface-active
Agent etc., while being also a kind of very strong organic solvent of solvability.In addition, having in 7-oxa-bicyclo[4.1.0 molecular structure very active
Epoxy group exists, can with the substance reactions such as ammonia, amine, phenol, alcohol, carboxylic acid and generate a series of compound.And all kinds ofization
Closing object has very high added value.
Early in late nineteen seventies, the Nuo Ge Plutarch chemical company in the U.S. just develops cyclohexene oxide production 7-oxa-bicyclo[4.1.0
Technique.The technology of foreign countries' synthesis mainly has following four.First is that organic peroxy acid system.This method often uses peroxyformic acid or acetic acid
Oxidant is made, peroxy acid is unstable, easily decomposes, is not easy to store, and the reaction time is not easy to control.Second is that cyclohexene and HOCl addition,
It is condensed into again around-France.The process often generates a large amount of 1,2- cyclohexanediol, influences yield because needing strong acid catalyst in reaction.Three
It is hydrogen peroxide oxidation method.Though having many advantages, because unstable, easy resolution characteristic can only be suitable for catalysis oxidation molecular weight under low temperature
Lesser molecule, and need high activated catalyst.Fourth is that molecular oxygen oxidation method.Though the method thinks the development prospect for having certain,
It is larger to research and develop effective catalyst difficulty, at present only among the research and development of laboratory.7-oxa-bicyclo[4.1.0 is widely used, but American-European, day
This 7-oxa-bicyclo[4.1.0 process units is also less, is unable to satisfy the demand in market.
The 7-oxa-bicyclo[4.1.0 production method of domestic-developed is a variety of at present, but for scale industrial production it is main there are two types of
Technique.First is that commercial recovery method.Mainly cyclohexane oxidation production cyclohexanone when, due to hexamethylene deep oxidation can generate one
Quantitative lightweight waste oil.Contain about 35% 7-oxa-bicyclo[4.1.0 and 25% or so n-amyl alcohol in lightweight waste oil.Pass through the side of rectifying
Formula separates 7-oxa-bicyclo[4.1.0.Second is that chemical synthesis.Typically have hypochlorous acid method, organic peroxy acid system, peroxide passivation,
Oxygen method.There is low selective yield, pollution weight, complex process etc. in hypochlorous acid method, organic peroxy acid system, oxygen method, it is naughty to face
The trend eliminated.Wherein environmentally protective with its using hydrogen peroxide as the new process of the cyclohexene oxide of oxidant production 7-oxa-bicyclo[4.1.0,
High income reacts the great interest that the advantageous features such as mild cause scientific research personnel, but current is in laboratory development phase,
There are no large-scale industrial productions.The 7-oxa-bicyclo[4.1.0 factory of China's scale has 3: the prosperous limited public affairs of Dehua work in Yueyang
Department, Long Xing industrial corporation, Yueyang general petrochemicals factory, the highly dense silver-colored limited liability company in Shandong.The wherein prosperous Dehua work industry of yueyang, hunan has
Limit company, unit scale are 1000 tons/year；Long Xing industrial corporation, Yueyang general petrochemicals factory, unit scale deficiency are 100 tons/year；Mountain
Dong Gaomiyin limited liability company, unit scale are 500 tons/year.As it can be seen that the 7-oxa-bicyclo[4.1.0 process units ability in China has
Limit, and production technology is more traditional.If the prosperous moral invention hexamethylene in Yueyang prepares the technique of 7-oxa-bicyclo[4.1.0, be by hexamethylene with
The gas reaction of molecule-containing keto prepares cyclohexyl hydroperoxide without catalysis or cobalt salt catalysis oxidation wherein can be used.Contain above-mentioned
The mixed liquor and cyclohexene of cyclohexyl hydroperoxide carry out oxidation reaction, use molybdenum class, tungsten class or vanadium class in the epoxidation
One of compound is catalyst preparation 7-oxa-bicyclo[4.1.0, and the dehydration of cyclohexanol that epoxidation reaction is generated generates cyclohexene,
It is recycled as one of epoxidised raw material.As it can be seen that the process flow is long, production process is complicated, and catalyst recycling is tired
Difficulty limits the technique extensive development.
In " Zhejiang Polytechnical University's journal " " new technique for synthesizing of 7-oxa-bicyclo[4.1.0 is studied ", it is condensed by sodium tungstate and phosphoric acid,
It is compounded again with quaternary ammonium salt cationic and obtains the epoxidation catalysts with high catalytic activity, using cyclohexene as raw material, with
Low concentration H2O2For oxygen source, reaction condition has been investigated.Optimizing preferable epoxidation reaction condition is catalyst: cyclohexene: H2O2
=1:200:130, reaction temperature be 50~60 DEG C, pH=3.5~5.5,1~4 h of time, cyclohexene conversion rate be 40%~
50%, H2O2Utilization rate is 80%, and 7-oxa-bicyclo[4.1.0 yield is 80%~85%.The experiment cyclohexene conversion ratio is lower, and produces
Object 7-oxa-bicyclo[4.1.0 yield is lower, uneconomical, is unable to further genralrlization application." cyclohexene liquid in " colleges and universities' chemical engineering journal "
Phase epoxidation synthesis epoxy cyclohexane " has synthesized molybdenum (VI) and has closed acetylacetone,2,4-pentanedione catalyst, investigated reaction mass proportion, solvent
Influence of the factors such as dosage, catalyst amount, reaction temperature, time to epoxidation synthesis process.The synthetic technological condition of optimization
For the molar ratio of cyclohexene and cumyl hydroperoxide is 3:1, is calculated with 0.04 mole of cumyl hydroperoxide, and solvent is
10ml closes acetylacetone,2,4-pentanedione catalyst 0.1g with molybdenum (VI), and reaction temperature is 80 DEG C, reaction time 60min, different with hydrogen peroxide
Propyl benzene calculates, and 7-oxa-bicyclo[4.1.0 yield is 99% or more, purity about 99.9%.But the experiment is only at Laboratory batch lab scale
Stage, and catalyst cannot recycle use.
As it can be seen that in order to which 7-oxa-bicyclo[4.1.0 is mass produced, and seek a kind of Atom economy height, green non-pollution, development
Potentiality are larger, and the 7-oxa-bicyclo[4.1.0 preparation method that can be promoted and applied is that have very much realistic meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0.Titanium molecular sieve catalysis
Agent be convenient for recycling and reusing, it is environmentally protective, and catalysis cyclohexene and cumyl hydroperoxide oxidation reaction process in, activity compared with
Good, product 7-oxa-bicyclo[4.1.0 selectivity is high, and reaction condition is mild, convenient for control.The method solves traditional industry and prepares epoxy hexamethylene
There is the shortcomings that selectivity is low with yield, pollution weighs, complex process in alkane, have effects that environmentally protective, can promote the use of hexamethylene
Alkene aoxidizes in 7-oxa-bicyclo[4.1.0 industrial production processed.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0；In the cumene solution of cumyl hydroperoxide solute
In, using cumyl hydroperoxide as oxidant, cyclohexene oxide reaction prepares 7-oxa-bicyclo[4.1.0, and catalyst is with central hole structure
Titanium Sieve Molecular Sieve.
Catalyst is applied in continuous fixed bed reaction or continuous, and fixed bed reaction condition is that cyclohexene and cumyl hydroperoxide are molten
The molar ratio of matter is (2.0~12.0): 1；Cumyl hydroperoxide feed weight air speed is 0.5~2.0h-1, reaction pressure is
0.2~3.0MPa, temperature are 40.0~120.0 DEG C.
In the present invention, there is diffraction maximum on X-ray diffraction spectrogram low-angle in the catalyst Ti-si molecular sieves, average hole
Diameter is 2.0~30.0nm, and specific surface area is 500.0~1200.0m2/g。
In the present invention, the catalyst Ti-si molecular sieves are one of Ti/MCM-41, Ti/HMS, Ti/MSU.
It is bar shaped or spherical shape after the catalyst Ti-si molecular sieves molding in the present invention.
In the present invention, the catalyst Ti-si molecular sieves intensity is 40-200N/cm.
In the present invention, the catalyst Ti-si molecular sieves bulk density is 0.4-0.6g/ml.
In the present invention, the cumene solution of the cumyl hydroperoxide solute of certain mass score, Solute mass fraction
For 15~50 wt%.
Advantages of the present invention: compared with existing 7-oxa-bicyclo[4.1.0 industrial technology, catalyst is easily recycled, green non-pollution.
And the good catalyst activity, 7-oxa-bicyclo[4.1.0 selectivity is high, and catalyst stability is higher, good economy performance, has preferable application
Effect can promote the use of in 7-oxa-bicyclo[4.1.0 industrial production.
Specific embodiment
The present invention is further elaborated by the following examples.
Embodiment 1
It is 2.1nm, specific surface area 1198.6m by aperture2The Titanium Sieve Molecular Sieve Ti/MCM-41 of/g is formed, molding
Titanium Sieve Molecular Sieve intensity is 40N/cm, bulk density 0.5g/ml afterwards, by molding bar shaped catalyst and a certain amount of quartz sand
It is uniformly mixed, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the mistake of 15wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of hydrogen oxide isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 2.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 0.5h-1, fixed bed reactors pressure is maintained into 0.2MPa, reaction temperature is controlled 40.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 2
It is 2.1nm, specific surface area 1198.6m by aperture2The Titanium Sieve Molecular Sieve Ti/MCM-41 of/g is formed, molding
Titanium Sieve Molecular Sieve intensity is 70N/cm, bulk density 0.6g/ml afterwards, by molding spheric catalyst and a certain amount of quartz sand
It is uniformly mixed, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the mistake of 15wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of hydrogen oxide isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 2.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 0.5h-1, fixed bed reactors pressure is maintained into 0.2MPa, reaction temperature is controlled 40.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 3
It is 8.3nm, specific surface area 996.5m by aperture2The Titanium Sieve Molecular Sieve Ti/MCM-41 of/g is formed, after molding
Titanium Sieve Molecular Sieve intensity is 80N/cm, and bulk density 0.5g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 25wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 2.0:1, and hydrogen peroxide is different
Propyl benzene feed weight air speed is 0.5h-1, fixed bed reactors pressure is maintained into 0.4MPa, reaction temperature is controlled at 40.0 DEG C,
After 4h is reacted in continuous feed, it is different to calculate raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis for sampling analysis
The conversion ratio of propyl benzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 4
It is 8.3nm, specific surface area 996.5m by aperture2The Titanium Sieve Molecular Sieve Ti/MCM-41 of/g is formed, after molding
Titanium Sieve Molecular Sieve intensity is 80N/cm, and bulk density 0.5g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 25wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 2.0:1, and hydrogen peroxide is different
Propyl benzene feed weight air speed is 0.5h-1, fixed bed reactors pressure is maintained into 0.4MPa, reaction temperature is controlled at 60.0 DEG C,
After 4h is reacted in continuous feed, it is different to calculate raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis for sampling analysis
The conversion ratio of propyl benzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 5
It is 14.8nm, specific surface area 862.1m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 90N/cm, bulk density 0.4g/ml, and molding bar shaped catalyst is mixed with a certain amount of quartz sand
Uniformly, it is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxidating of 25wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 5.0:1, hydrogen peroxide isopropyl
Benzene feed weight air speed is 0.8h-1, fixed bed reactors pressure is maintained into 0.4MPa, reaction temperature is controlled at 60.0 DEG C, even
After continuous charging reaction 4h, sampling analysis calculates raw material hydrogen peroxide isopropyl by gas-chromatography and chemical iodimetric analysis
The conversion ratio of benzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 6
It is 14.8nm, specific surface area 862.1m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 90N/cm, bulk density 0.4g/ml, and molding bar shaped catalyst is mixed with a certain amount of quartz sand
Uniformly, it is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxidating of 25wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 5.0:1, hydrogen peroxide isopropyl
Benzene feed weight air speed is 0.8h-1, fixed bed reactors pressure is maintained into 1.0MPa, reaction temperature is controlled at 60.0 DEG C, even
After continuous charging reaction 4h, sampling analysis calculates raw material hydrogen peroxide isopropyl by gas-chromatography and chemical iodimetric analysis
The conversion ratio of benzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 7
It is 14.8nm, specific surface area 862.1m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 120N/cm, and bulk density 0.6g/ml mixes molding spheric catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 25wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 5.0:1, and hydrogen peroxide is different
Propyl benzene feed weight air speed is 0.8h-1, fixed bed reactors pressure is maintained into 1.0MPa, reaction temperature is controlled at 80.0 DEG C,
After 4h is reacted in continuous feed, it is different to calculate raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis for sampling analysis
The conversion ratio of propyl benzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 8
It is 23.7nm, specific surface area 754.7m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 100N/cm, and bulk density 0.5g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 10.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 0.8h-1, fixed bed reactors pressure is maintained into 1.0MPa, reaction temperature is controlled 80.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 9
It is 23.7nm, specific surface area 754.7m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 100N/cm, and bulk density 0.5g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 10.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 1.0h-1, fixed bed reactors pressure is maintained into 2.0MPa, reaction temperature is controlled 80.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 10
It is 23.7nm, specific surface area 754.7m by aperture2The Titanium Sieve Molecular Sieve Ti/HMS of/g is formed, titanium after molding
Si molecular sieves intensity is 100N/cm, and bulk density 0.5g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 10.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 1.0h-1, fixed bed reactors pressure is maintained into 2.0MPa, reaction temperature is controlled 100.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 11
It is 30.0nm, specific surface area 500.2m by aperture2The Titanium Sieve Molecular Sieve Ti/MSU of/g is formed, titanium after molding
Si molecular sieves intensity is 160N/cm, and bulk density 0.4g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 12.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 1.5h-1, fixed bed reactors pressure is maintained into 2.0MPa, reaction temperature is controlled 100.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 12
It is 30.0nm, specific surface area 500.2m by aperture2The Titanium Sieve Molecular Sieve Ti/MSU of/g is formed, titanium after molding
Si molecular sieves intensity is 160N/cm, and bulk density 0.4g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 12.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 1.5h-1, fixed bed reactors pressure is maintained into 3.0MPa, reaction temperature is controlled 100.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 13
It is 30.0nm, specific surface area 500.2m by aperture2The Titanium Sieve Molecular Sieve Ti/MSU of/g is formed, titanium after molding
Si molecular sieves intensity is 160N/cm, and bulk density 0.4g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 35wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 12.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 2.0h-1, fixed bed reactors pressure is maintained into 3.0MPa, reaction temperature is controlled 120.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 14
It is 30.0nm, specific surface area 500.2m by aperture2The Titanium Sieve Molecular Sieve Ti/MSU of/g is formed, titanium after molding
Si molecular sieves intensity is 160N/cm, and bulk density 0.4g/ml mixes molding bar shaped catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 50wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 12.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 2.0h-1, fixed bed reactors pressure is maintained into 3.0MPa, reaction temperature is controlled 120.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
Embodiment 15
It is 30.0nm, specific surface area 500.2m by aperture2The Titanium Sieve Molecular Sieve Ti/MSU of/g is formed, titanium after molding
Si molecular sieves intensity is 200N/cm, and bulk density 0.6g/ml mixes molding spheric catalyst and a certain amount of quartz sand
It closes uniformly, is loaded into the flat-temperature zone of fixed bed reactors.Cyclohexene and the peroxide of 50wt% are passed through in fixed bed reactors
The molar ratio of the cumene solution of change hydrogen isopropylbenzene solute, cyclohexene and cumyl hydroperoxide is 12.0:1, hydrogen peroxide
Isopropylbenzene feed weight air speed is 2.0h-1, fixed bed reactors pressure is maintained into 3.0MPa, reaction temperature is controlled 120.0
DEG C, after 4h is reacted in continuous feed, sampling analysis calculates raw material hydrogen peroxide by gas-chromatography and chemical iodimetric analysis
The conversion ratio of isopropylbenzene and the selectivity of product 7-oxa-bicyclo[4.1.0, the result is shown in tables 1.
1 titanium-silicon molecular sieve catalyst evaluation result of table
| Embodiment | Cumyl hydroperoxide conversion ratio % | 7-oxa-bicyclo[4.1.0 selectivity % |
| Embodiment 1 | 91.3 | 98.2 |
| Embodiment 2 | 90.6 | 98.1 |
| Embodiment 3 | 92.4 | 98.7 |
| Embodiment 4 | 96.3 | 98.9 |
| Embodiment 5 | 96.7 | 99.1 |
| Embodiment 6 | 98.4 | 99.2 |
| Embodiment 7 | 98.7 | 99.3 |
| Embodiment 8 | 98.9 | 99.6 |
| Embodiment 9 | 99.2 | 99.4 |
| Embodiment 10 | 99.8 | 99.9 |
| Embodiment 11 | 98.6 | 99.2 |
| Embodiment 12 | 99.1 | 99.3 |
| Embodiment 13 | 98.3 | 99.1 |
| Embodiment 14 | 97.6 | 98.5 |
| Embodiment 15 | 97.1 | 98.2 |
As it can be seen from table 1 using titanium-silicon molecular sieve catalyst, under certain condition, to contain 35wt% hydrogen peroxide
The cumene solution of isopropylbenzene solute is oxidant, and cyclohexene oxide prepares 7-oxa-bicyclo[4.1.0, the conversion of cumyl hydroperoxide
Rate can reach 99.8%, and the selectivity of 7-oxa-bicyclo[4.1.0 is up to 99.9%.It can be seen that the catalyst activity preferably, selectivity compared with
Height, and reaction condition is mild, has preferable technical effect, can promote the use of in industrial production.
Claims (8)
1. a kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0；In the cumene solution of cumyl hydroperoxide solute,
Using cumyl hydroperoxide as oxidant, cyclohexene oxide reaction prepares 7-oxa-bicyclo[4.1.0, and catalyst is with central hole structure
Titanium Sieve Molecular Sieve.
2. the method as described in claim 1, it is characterized in that catalyst is applied in continuous fixed bed reaction or continuous, fixed bed reaction item
Part is that the molar ratio of cyclohexene and cumyl hydroperoxide solute is (2.0~12.0): 1；Cumyl hydroperoxide feed weight
Air speed is 0.5~2.0h-1, reaction pressure is 0.2~3.0MPa, and temperature is 40.0~120.0 DEG C.
3. the method as described in claim 1, it is characterized in that the catalyst Ti-si molecular sieves are in X-ray diffraction spectrogram low-angle
On there is diffraction maximum, average pore size is 2.0~30.0nm, and specific surface area is 500.0~1200.0m2/g。
4. the method as described in claim 1, it is characterized in that the catalyst Ti-si molecular sieves be Ti/MCM-41, Ti/HMS or
One of Ti/MSU.
5. the method as described in claim 1, it is characterized in that being bar shaped or spherical shape after catalyst Ti-si molecular sieves molding.
6. the method as described in claim 1, it is characterized in that the catalyst Ti-si molecular sieves intensity is 40-200N/cm.
7. the method as described in claim 1, it is characterized in that the catalyst Ti-si molecular sieves bulk density is 0.4-0.6g/
ml。
8. the method as described in claim 1, it is characterized in that the cumene solution of cumyl hydroperoxide solute, Solute mass
Score is 15~50wt%.
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