CN106588821A - Method of preparing cyclohexene oxide by oxidizing cyclohexene with oxygen under low temperature plasmas - Google Patents
Method of preparing cyclohexene oxide by oxidizing cyclohexene with oxygen under low temperature plasmas Download PDFInfo
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- CN106588821A CN106588821A CN201611008781.4A CN201611008781A CN106588821A CN 106588821 A CN106588821 A CN 106588821A CN 201611008781 A CN201611008781 A CN 201611008781A CN 106588821 A CN106588821 A CN 106588821A
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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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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Abstract
The invention discloses a method of preparing cyclohexene oxide by oxidizing cyclohexene with oxygen under low temperature plasmas. The method comprises the following steps: firstly, putting a low temperature plasma reactor into a constant temperature device, heating, and controlling the temperature; introducing argon into a cyclohexene constant-temperature bottle with a constant temperature and a saturated vapor pressure, and enabling argon to enter a gas inlet formed in the reactor by carrying cyclohexene steam; in addition, introducing oxygen as an oxidant into the gas inlet formed in the reactor; introducing the two gases into the reactor simultaneously; when flow rates of the argon and the oxygen reach stable, regulating an electrode gap between two electrodes of the reactor, turning on a low temperature plasma power supply, regulating input power of the reactor and the pressure of the reactor to normal pressure, and carrying out reaction on the cyclohexene steam carried by the argon and the oxygen under the condition; discharging an obtained product from a gas outlet of the reactor, and collecting the product; and enabling residual gas to enter a tail gas absorption device. The method is mild in condition, simple to operate, high in atom economy and clean in reaction without pollution and prepares the cyclohexene oxide by oxidizing the cyclohexene with the oxygen at a normal temperature and a normal pressure.
Description
Technical field
The present invention relates to a kind of preparation method of 7-oxa-bicyclo[4.1.0, and in particular to dioxygen oxidation under a kind of low temperature plasma
The method that cyclohexene prepares 7-oxa-bicyclo[4.1.0.
Background technology
The aggregate that plasma is made up of particulates such as the various particles with positive and negative charge and various active groups, it is overall
Upper is in electroneutral, is the 4th state of material.When applied voltage reaches the firing voltage of gas, gas molecule is breakdown, produces
Including the mixture including electronics, various ions, atom and free radical.The high-energy of low temperature plasma electronics can excite, from
Solution and ionization reaction thing molecule, and reaction system can keep low temperature, even close room temperature, reduce reaction system energy consumption.Cause
This, low temperature plasma is in chemical reaction using quite varied.
7-oxa-bicyclo[4.1.0, fusing point is -40 DEG C, and boiling point is 130-132 DEG C, a kind of colourless or weak yellow liquid with fragrance,
It is water insoluble, can mix with the volatile substance such as ethanol, ether, acetone.7-oxa-bicyclo[4.1.0 is important organic synthesis intermediate, in system
Standby agricultural chemicals gram wax spy, nylon66 fiber, adipic acid, epoxy resin coating, rubber accelerator, dyestuff, medicine, material, surfactant are wide
It is general to use.The very strong organic solvent of 7-oxa-bicyclo[4.1.0 or solvability;7-oxa-bicyclo[4.1.0 has the characteristic of photosensitive polymerization, can enter
Row transparent bonding and low temperature bonding, can be used as photoactive coating and photosensitive binder.
At present, the process route of epoxidation of cyclohexene synthesis epoxy cyclohexane, according to the difference of oxidant have hypohalogenous acids method,
Iodosobenzene method, iodosobenzene method and alkyl peroxide method.It is low to there is raw material availability in above conventional method, environmental pollution
Serious the shortcomings of.With the continuous improvement to cleaner Production in Chemical Industry technical requirements, " green chemical industry " technology synthesizing epoxy ring is adopted
Hexane meets the needs of sustainable development and environmental friendliness strategy.
The content of the invention
The technical problem to be solved in the present invention is:Molecular oxygen oxidation cyclohexene under a kind of low temperature plasma is provided and prepares ring
The method of oxygen hexamethylene.The inventive method mild condition, simple to operate, Atom economy are high and react clean pollution-free, can be
Realize that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0, and the selectivity of 7-oxa-bicyclo[4.1.0 up to 69% under normal temperature and pressure, first is secondary
The selectivity of product cyclohexanone is up to 24%.
In order to solve the above problems, the present invention is adopted the technical scheme that:
The present invention provides a kind of method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma, the preparation side
Method is comprised the following steps:
A, raw material liq cyclohexene is placed in constant temperature bottle first, the thermostat temperature for adjusting liquid cyclohexene is 25~50 DEG C;Will
Reaction of low temperature plasma device is placed in thermostat, and the temperature of computer heating control reaction of low temperature plasma device is 25~65 DEG C;
In b, the constant temperature bottle equipped with liquid cyclohexene for argon gas being passed through 25~50 DEG C of constant temperature, reaching under the conditions of saturated vapour pressure,
The air inlet that argon gas is provided with by conduit with the speed that flow is 300~700mL/min into reaction of low temperature plasma device;
C, it is that the oxidant oxygen of 200~500mL/min is provided with by conduit into reaction of low temperature plasma device by flow
Air inlet;
D, the argon gas of carrying cyclohexene steam and oxygen converge in reaction of low temperature plasma device air inlet, while being passed through low temperature etc.
In plasma reactor, two strands of gases are kept to be continually fed into 30~60min, now argon gas and oxygen flow reach stable, hexamethylene
Alkene steam and oxygen mix are uniform;
E, the then interelectrode electrode gap of regulation reaction of low temperature plasma device two are 12.4~16mm, open low-temperature plasma
Body power supply, it is 45~75 W to adjust reaction of low temperature plasma device input power, and plasma reactor is normal pressure, is taken by argon gas
The cyclohexene steam of band and oxygen are reacted with this understanding, and the reaction time is 30~120 s;
After f, reaction terminate, gained gas products are discharged from the gas outlet of reaction of low temperature plasma device, are collected after discharge,
Then it is analyzed using gas chromatographicanalyzer, residual gas is processed into device for absorbing tail gas.
According to the method that dioxygen oxidation cyclohexene under above-mentioned low temperature plasma prepares 7-oxa-bicyclo[4.1.0, described low temperature etc.
Plasma reactor is flat reaction of low temperature plasma device, and buffer layer adopts quartz medium, the thickness of quartz medium
For 3mm, the equal 80mm of diameter;The electrode for adopting is smooth cylindrical metal aluminium electrode, a diameter of 50mm.
According to the method that dioxygen oxidation cyclohexene under above-mentioned low temperature plasma prepares 7-oxa-bicyclo[4.1.0, the oxidant
Purity >=99.99% of oxygen.
According to the method that dioxygen oxidation cyclohexene under above-mentioned low temperature plasma prepares 7-oxa-bicyclo[4.1.0, argon in step b
It is 0.030~0.115 g/min that gas carries the mass flow of cyclohexene steam.
The positive beneficial effect of the present invention:
1st, under low-temperature plasma of the present invention cyclohexene with oxygen as oxidant epoxidation synthesis epoxy cyclohexane, be a green,
The high syntheti c route of Atom economy;I.e. the invention provides a kind of high-efficiency environment friendly method for preparing 7-oxa-bicyclo[4.1.0.
2nd, the present invention is with oxygen O2It is abundant raw material, cheap for oxidant, but molecular oxygen Stability Analysis of Structures, but conventional feelings
It is very difficult that condition oxygen is directly used in cyclohexene oxide, needs to develop special catalyst, relatively costly.The present invention adopts plasma
Body auxiliary synthesis can significantly reduce the activation energy of reaction, be entirely capable of making oxygen direct oxidation cyclohexene without catalyst, have
The gentle advantage of low energy consumption, high-effect, environmental friendliness, reaction.Therefore, the present invention has significant economic benefit and society's effect
Benefit.
3rd, the present invention is first dioxygen oxidation cyclohexene to be combined into the advantage of low temperature plasma, under low temperature plasma
The dioxygen oxidation for carrying out cyclohexene prepares the method for 7-oxa-bicyclo[4.1.0, and utilization is the method achieved at normal temperatures and pressures by hexamethylene
Alkene directly prepares the purpose of 7-oxa-bicyclo[4.1.0.
4th, by technical solution of the present invention, can at normal temperatures and pressures realize that dioxygen oxidation cyclohexene prepares epoxy hexamethylene
Alkane, the conversion ratio of cyclohexene can reach 59%, and the selectivity of 7-oxa-bicyclo[4.1.0 can reach 69%, the choosing of the first by-product cyclic hexanone
Selecting property is up to 24%.Preparation method of the present invention is simple to operate, mild condition, it is easy to accomplish, energy saving has a extensive future.
Description of the drawings:
The GC-MS spectrograms of Fig. 1 products obtained therefroms of the present invention;
The mass spectrogram of gained 7-oxa-bicyclo[4.1.0 after Fig. 2 products obtained therefrom makings separation of the present invention;
The GC-MS database matching analysis results of Fig. 3 products obtained therefroms of the present invention;
The gas chromatogram of Fig. 4 7-oxa-bicyclo[4.1.0 sterlings;
The gas chromatogram of Fig. 5 products obtained therefroms of the present invention;
In Fig. 5:Cyclohexene t1=3.002,7-oxa-bicyclo[4.1.0 t2=5.751, cyclohexanone t3=6.542。
The gas chromatogram of the products obtained therefrom of Fig. 6 embodiment of the present invention 1;
The gas chromatogram of the products obtained therefrom of Fig. 7 embodiment of the present invention 2;
The gas chromatogram of the products obtained therefrom of Fig. 8 embodiment of the present invention 3;
The gas chromatogram of the products obtained therefrom of Fig. 9 embodiment of the present invention 4;
The gas chromatogram of the products obtained therefrom of Figure 10 embodiment of the present invention 5;
The present invention is using Agilent-7890A types GC-MS to the dioxygen oxidation cyclohexene of embodiment of the present invention plasma treatment
Gas-phase product is analyzed(Mass spectrograph condition:Electron ionization voltage be 70eV, electron impact ionization(EI), emission current
60 μ V, carrier gas:High-purity helium, mass range m/Z:86~450, ion source temperature:230 DEG C, interface temperature:250 ℃), GC
Spectrogram is as shown in Figure 1.The mass spectrogram of the GC separation products of retention time t=3.142(Accompanying drawing 2)The analysis shows product is doubtful
Standard spectrum for 7-oxa-bicyclo[4.1.0, based on the search in similarity mode storehouse, in the signal peak collected by mass spectrum and database
Figure compares, its qualitative analysis(Accompanying drawing 3)Show the 7-oxa-bicyclo[4.1.0 in the mass spectrogram and NTSB08 databases of the material
Spectrogram similarity reach 95%.To further determine that the product, verified using standard items.
The basic foundation of chromatographic qualitative analysis is retention time, under certain chromatographic condition, a material only one of which
Retention time, unknown material is compared with the retention time of pure material, can initial characterization identification unknown material.In same chromatostrip
Under part, purchase in Ourchem (CAS numberings:286-20-4) retention time t=of the 7-oxa-bicyclo[4.1.0 gas phase standard items of company
5.802 (accompanying drawing 3), hand sampling time error is excluded, under same chromatographic condition, when the retention time of the standard items is with retaining
Between t=5.751 reaction principal product retention time it is basically identical.
With reference to GC-MS and GC the qualitative analysis it was determined that dioxygen oxidation cyclohexene under low temperature plasma of the present invention
The product that mainly generates of reaction is 7-oxa-bicyclo[4.1.0.
The gas chromatographic analysis figure of Fig. 6-10 embodiment of the present invention 1-5 products therefroms;The conversion ratio of cyclohexene and product
It is selective peak area is corrected based on peak area quantification analysis, and the correction factor using each material.
Specific embodiment:
The present invention is expanded on further with reference to embodiments, but is not intended to limit present disclosure.
The reaction of low temperature plasma device adopted in following examples is flat reaction of low temperature plasma device, medium every
Absciss layer adopts quartz medium, and the thickness of quartz medium is 3mm, the equal 80mm of diameter;The electrode for adopting is smooth cylindrical metallic aluminium
Electrode, a diameter of 50mm.
Using oxidant oxygen purity >=99.99%.
Embodiment 1:
The method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma of the present invention, the detailed step of the preparation method
It is rapid as follows:
A, the mL of raw material liq cyclohexene 150 is placed in constant temperature bottle first, the thermostat temperature for adjusting liquid cyclohexene is 40 DEG C;
Reaction of low temperature plasma device is placed in thermostat, the temperature of computer heating control reaction of low temperature plasma device is 30 DEG C;
In b, the constant temperature bottle equipped with liquid cyclohexene for argon gas being passed through 40 DEG C of constant temperature, reaching under the conditions of saturated vapour pressure, argon gas
The air inlet that speed with flow as 500mL/min is provided with by conduit into reaction of low temperature plasma device, argon gas carries ring
The mass flow of hexene steam is 0.072 g/min;
C, the air inlet for being provided with flow into reaction of low temperature plasma device by conduit for the oxidant oxygen of 300mL/min
Mouthful;
D, the argon gas of carrying cyclohexene steam and oxygen converge in reaction of low temperature plasma device air inlet, while being passed through low temperature etc.
In plasma reactor, two strands of gases are kept to be continually fed into 30 min, now argon gas and oxygen flow reach stable, cyclohexene steaming
Vapour and oxygen mix are uniform;
E, the interelectrode electrode gap of regulation reaction of low temperature plasma device two are 12.4 mm, open low-temperature plasma electrical source,
It is 57.0 W to adjust reaction of low temperature plasma device input power, and plasma reactor is normal pressure, the hexamethylene carried by argon gas
Alkene steam and oxygen are reacted with this understanding, and the reaction time is 30s;
After f, reaction terminate, gained gas products are discharged from the gas outlet of reaction of low temperature plasma device, are collected after discharge,
Then it is analyzed using gas chromatographicanalyzer, residual gas enters device for absorbing tail gas.
Product analysis:Gained 7-oxa-bicyclo[4.1.0 gas products are analyzed by gas chromatographicanalyzer, cyclohexene conversion
Rate is 59.06%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 68.70%, and the selectivity of the first by-product cyclic hexanone is 22.32%;Gas phase color
Analysis of spectrum result is as shown in Figure 6.
Embodiment 2:Substantially the same manner as Example 1, difference is:
The method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma of the present invention, the preparation method and embodiment
1 difference is:
In step a:The thermostat temperature for adjusting liquid cyclohexene is 25 DEG C;Reaction of low temperature plasma device is placed in into thermostat
In, the temperature of computer heating control reaction of low temperature plasma device is 50 DEG C;
In step b:Argon gas is passed through 25 DEG C of constant temperature, reaches the constant temperature bottle equipped with liquid cyclohexene under the conditions of saturated vapour pressure
In, the air inlet that speed of the argon gas with flow as 700mL/min is provided with by conduit into reaction of low temperature plasma device, argon gas
The mass flow for carrying cyclohexene steam is 0.115 g/min;
In step c:The oxidant oxygen that flow is 200 mL/min is provided with by conduit into reaction of low temperature plasma device
Air inlet;
In step d:Two strands of gases are kept to be continually fed into 40 min;
In step e:It is 16.0 mm to adjust the interelectrode electrode gap of reaction of low temperature plasma device two, opens low-temperature plasma
Body power supply, it is 75.0 W to adjust reaction of low temperature plasma device input power.
Product analysis:Gained 7-oxa-bicyclo[4.1.0 gas products are analyzed by gas chromatographicanalyzer, cyclohexene conversion
Rate is 51.47%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 58.31%, and the selectivity of the first by-product cyclic hexanone is 20.21%;Gas phase color
Analysis of spectrum result is as shown in Figure 7.
Embodiment 3:Substantially the same manner as Example 1, difference is:
The method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma of the present invention, the preparation method and embodiment
1 difference is:
In step a:The thermostat temperature for adjusting liquid cyclohexene is 50 DEG C;Reaction of low temperature plasma device is placed in into thermostat
In, the temperature of computer heating control reaction of low temperature plasma device is 25 DEG C;
In step b:Argon gas is passed through 50 DEG C of constant temperature, reaches the constant temperature bottle equipped with liquid cyclohexene under the conditions of saturated vapour pressure
In, the air inlet that argon gas is provided with by conduit with the speed that flow is 300 mL/min into reaction of low temperature plasma device;Argon
It is 0.030 g/min that gas carries the mass flow of cyclohexene steam;
In step c:The oxidant oxygen that flow is 500 mL/min is provided with by conduit into reaction of low temperature plasma device
Air inlet;
In step d:Two strands of gases are kept to be continually fed into 60 min;
In step e:Low-temperature plasma electrical source is opened, it is 45 W to adjust reaction of low temperature plasma device input power;During reaction
Between be 120 s.
Product analysis:Gained 7-oxa-bicyclo[4.1.0 gas products are analyzed by gas chromatographicanalyzer, cyclohexene conversion
Rate is 48.02%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 69.06%, and the selectivity of the first by-product cyclic hexanone is 20.44%.Gas phase color
Analysis of spectrum result is as shown in Figure 8.
Embodiment 4:Substantially the same manner as Example 1, difference is:
The method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma of the present invention, the preparation method and embodiment
1 difference is:
In step a:The thermostat temperature for adjusting liquid cyclohexene is 30 DEG C;Reaction of low temperature plasma device is placed in into thermostat
In, the temperature of computer heating control reaction of low temperature plasma device is 45 DEG C;
In step b:Argon gas is passed through 30 DEG C of constant temperature, reaches the constant temperature bottle equipped with liquid cyclohexene under the conditions of saturated vapour pressure
In, the air inlet that speed of the argon gas with flow as 450mL/min is provided with by conduit into reaction of low temperature plasma device, argon gas
The mass flow for carrying cyclohexene steam is 0.065 g/min;
In step c:The oxidant oxygen that flow is 400 mL/min is provided with by conduit into reaction of low temperature plasma device
Air inlet;
In step d:Two strands of gases are kept to be continually fed into 50 min;
In step e:It is 15.0 mm to adjust the interelectrode electrode gap of reaction of low temperature plasma device two, opens low-temperature plasma
Body power supply, it is 66.5W to adjust reaction of low temperature plasma device input power;Reaction time is 60 s.
Product analysis:Gained 7-oxa-bicyclo[4.1.0 gas products are analyzed by gas chromatographicanalyzer, cyclohexene conversion
Rate is 53.00%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 68.75%, and the selectivity of the first by-product cyclic hexanone is 19.86%.Gas phase color
Analysis of spectrum result is as shown in Figure 9.
Embodiment 5:Substantially the same manner as Example 1, difference is:
The method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma of the present invention, the preparation method and embodiment
1 difference is:
In step a:The thermostat temperature for adjusting liquid cyclohexene is 30 DEG C;Reaction of low temperature plasma device is placed in into thermostat
In, the temperature of computer heating control reaction of low temperature plasma device is 65 DEG C;
In step b:Argon gas is passed through 30 DEG C of constant temperature, reaches the constant temperature bottle equipped with liquid cyclohexene under the conditions of saturated vapour pressure
In, the air inlet that speed of the argon gas with flow as 400mL/min is provided with by conduit into reaction of low temperature plasma device;Argon gas
The mass flow for carrying cyclohexene steam is 0.043 g/min;
In step d:Two strands of gases are kept to be continually fed into 40 min;
In step e:It is 13.5 mm to adjust the interelectrode electrode gap of reaction of low temperature plasma device two;Reaction time is 60s.
Product analysis:Gained 7-oxa-bicyclo[4.1.0 gas products are analyzed by gas chromatographicanalyzer, cyclohexene conversion
Rate is 51.91%, and the selectivity of 7-oxa-bicyclo[4.1.0 is 65.05%, and the selectivity of the first by-product cyclic hexanone is 24.04%.Gas phase color
Analysis of spectrum result is as shown in Figure 10.
Claims (4)
1. a kind of method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma, it is characterised in that the system
Preparation Method is comprised the following steps:
A, raw material liq cyclohexene is placed in constant temperature bottle first, the thermostat temperature for adjusting liquid cyclohexene is 25~50 DEG C;Will
Reaction of low temperature plasma device is placed in thermostat, and the temperature of computer heating control reaction of low temperature plasma device is 25~65 DEG C;
In b, the constant temperature bottle equipped with liquid cyclohexene for argon gas being passed through 25~50 DEG C of constant temperature, reaching under the conditions of saturated vapour pressure,
The air inlet that argon gas is provided with by conduit with the speed that flow is 300~700mL/min into reaction of low temperature plasma device;
C, it is that the oxidant oxygen of 200~500mL/min is provided with by conduit into reaction of low temperature plasma device by flow
Air inlet;
D, the argon gas of carrying cyclohexene steam and oxygen converge in reaction of low temperature plasma device air inlet, while being passed through low temperature etc.
In plasma reactor, two strands of gases are kept to be continually fed into 30~60min, now argon gas and oxygen flow reach stable, hexamethylene
Alkene steam and oxygen mix are uniform;
E, the then interelectrode electrode gap of regulation reaction of low temperature plasma device two are 12.4~16mm, open low-temperature plasma
Body power supply, it is 45~75 W to adjust reaction of low temperature plasma device input power, and plasma reactor is normal pressure, is taken by argon gas
The cyclohexene steam of band and oxygen are reacted with this understanding, and the reaction time is 30~120 s;
After f, reaction terminate, gained gas products are discharged from the gas outlet of reaction of low temperature plasma device, are collected after discharge,
Then it is analyzed using gas chromatographicanalyzer, residual gas is processed into device for absorbing tail gas.
2. the method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma according to claim 1, its
It is characterised by:The reaction of low temperature plasma device is flat reaction of low temperature plasma device, and buffer layer is using quartz
Medium, the thickness of quartz medium is 3mm, the equal 80mm of diameter;The electrode for adopting is smooth cylindrical metal aluminium electrode, a diameter of
50mm。
3. the method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma according to claim 1, its
It is characterised by:Purity >=99.99% of the oxidant oxygen.
4. the method that dioxygen oxidation cyclohexene prepares 7-oxa-bicyclo[4.1.0 under low temperature plasma according to claim 1, its
It is characterised by:The mass flow that argon gas carries cyclohexene steam in step b is 0.030~0.115 g/min.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1546368A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for directly synthesizing hydrogen peroxide at room temperature for epoxidation of propylene |
CN1546479A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for epoxidation of propylene using plasma of hydrogen and oxygen |
CN1587262A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | High voltage discharge reactor and method for directly synthesizing epoxy propane from propene and oxygen |
CN101020670A (en) * | 2007-03-17 | 2007-08-22 | 大连海事大学 | Apparatus for direct oxidization of propane with molecular oxygen to prepare propane epoxide |
US20110275842A1 (en) * | 2010-05-10 | 2011-11-10 | Hoflund Gar B | Nanostructured catalyst pellets, catalyst surface treatment and highly selective catalyst for ethylene epoxidation |
CN105541571A (en) * | 2015-12-15 | 2016-05-04 | 浙江工商大学 | Method for preparing oxygen-containing organic compounds by plasma discharge |
-
2016
- 2016-11-16 CN CN201611008781.4A patent/CN106588821B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1546368A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for directly synthesizing hydrogen peroxide at room temperature for epoxidation of propylene |
CN1546479A (en) * | 2003-11-28 | 2004-11-17 | 大连理工大学 | Method and device for epoxidation of propylene using plasma of hydrogen and oxygen |
CN1587262A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | High voltage discharge reactor and method for directly synthesizing epoxy propane from propene and oxygen |
CN101020670A (en) * | 2007-03-17 | 2007-08-22 | 大连海事大学 | Apparatus for direct oxidization of propane with molecular oxygen to prepare propane epoxide |
US20110275842A1 (en) * | 2010-05-10 | 2011-11-10 | Hoflund Gar B | Nanostructured catalyst pellets, catalyst surface treatment and highly selective catalyst for ethylene epoxidation |
CN105541571A (en) * | 2015-12-15 | 2016-05-04 | 浙江工商大学 | Method for preparing oxygen-containing organic compounds by plasma discharge |
Non-Patent Citations (4)
Title |
---|
D.D.TANNER等: "Reactions of Microwave-Generated O(3P) Atoms with Unsaturated Hydrocarbons", 《J.ORG.CHEM.》 * |
杨丹红等: "环己烯催化环氧化合成环氧环己烷反应研究", 《应用化工》 * |
郭明星等: "丙烯和氧等离子体直接气相合成环氧丙烷", 《高等学校化学学报》 * |
郭明星等: "冷等离子体条件下分子氧丙烯气相环氧化", 《现代化工》 * |
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