CN108774198A - A kind of method that toluene conjugated oxidation prepares propylene oxide - Google Patents
A kind of method that toluene conjugated oxidation prepares propylene oxide Download PDFInfo
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- CN108774198A CN108774198A CN201810816769.9A CN201810816769A CN108774198A CN 108774198 A CN108774198 A CN 108774198A CN 201810816769 A CN201810816769 A CN 201810816769A CN 108774198 A CN108774198 A CN 108774198A
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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
- C07D301/19—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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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
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Abstract
The invention discloses a kind of methods that toluene conjugated oxidation prepares propylene oxide.Using toluene, molecular oxygen and propylene as raw material, propylene oxide is prepared by toluene oxidation unit, epoxidation of propylene unit, de- light component unit, de- propylene units, de- propylene oxide units, propylene oxide refined unit.The benzyl hydrogen peroxide that the present invention is generated using toluene oxidation provides peroxide as epoxidation of propylene, and the conversion ratio in propylene peroxidization is more than 99.0%, and the yield of propylene oxide is more than 95%, and the purity of propylene oxide is more than 99.5%；The present invention have production cost it is low, safe, low energy consumption, and technological process is short, and operating cost is low, and equipment investment is low, it is environmentally protective the advantages that.
Description
Technical field
The present invention relates to a kind of preparation method of organic matter, particularly as being that a kind of toluene conjugated oxidation prepares ring
The method of Ethylene Oxide.
Background technology
Propylene oxide（PO）It is the third-largest acryloyl derivative in addition to polypropylene and acrylonitrile, is important and organises substantially
Work raw material, mainly for the production of polyethers, propylene glycol etc., while it is also forth generation detergent nonionic surfactant, oil field
The primary raw material of demulsifier, farm chemical emulgent etc..The derivative of PO is widely used in automobile, building, food, tobacco, medicine and change
The industries such as cosmetic.Current industrialized propylene oxide production process has：Chlorohydrination, conjugated oxidation and direct oxidation method.Chloropharin
Method is to obtain propylene oxide after chlorohydrination, saponification, subtractive process using propylene and chlorine as raw material, but produced in production process
Raw a large amount of chlorine-contained wastewater, pollutes environment, equipment seriously corroded.Conjugated oxidation is divided into ethylbenzene hydroperoxide method according to raw material difference
(PO/SM methods), iso-butane hydrogen peroxide method (PO/TBA methods) and cumyl hydroperoxide method (CHP methods), conjugated oxidation overcomes
The shortcomings of existing pollution of chlorohydrination and corrosion, but long flow path, investment is big, co-product is more, since joint product are more, to a certain degree
On affect the production of propylene oxide.Direct oxidation method is propylene and H2O2In the presence of special Ti-Si catalyst, directly react
Propylene oxide is generated, the advantage of this process is that without the generation of coproduction product, simple for process, cost of investment is low and environmentally protective, is existed
The shortcomings that be H2O2Costly and amount transport it is inconvenient, need that nearby construction production capacity is comparable at propylene oxide unit scene
H2O2Device.In view of this, the production technology to propylene oxide conducts a research, better preparation method is found, the sector is become
Brainstorm subject.
Invention content
The object of the present invention is to provide one kind using toluene and propylene as raw material, and epoxy is prepared using conjugated oxidation
The method of propane, overcomes the deficiencies in the prior art.
The present invention solves its technical problem and adopts the technical scheme that such, and a kind of toluene conjugated oxidation prepares epoxy third
The method of alkane, includes the following steps：
（1）Toluene oxidation unit
Toluene is added in oxidizing reactor after pretreatment respectively with molecular oxygen, and in oxidation catalyst, initiator, auxiliary agent, there are items
Oxidation reaction is carried out under part, generates the oxidation liquid of mainly hydrogen peroxide containing benzyl, benzyl alcohol, benzaldehyde and toluene；
Wherein, it is preferred that toluene is 0.8~2.6 MPa with molecular oxygen respective pretreatment to pressure, and temperature is 120~250 oC；
Wherein, the type of molecular oxygen is one or more of air, pure oxygen, oxygen-enriched air or ozone；
Wherein, the pressure of oxidation reaction is 0.3~2.6 MPa, and temperature is 120~250 oC, the molar ratio of molecular oxygen and toluene
For (0.1~10):1, the residence time is 30~180 min, and oxidation catalyst is in cobalt naphthenate, cobalt acetate and cobalt benzoate
One or more, content be 0.1~20 ppm, initiator is benzyl peroxide, benzaldehyde, benzyl alcohol, benzoic acid and mistake
One or more of hydrogen oxide, content are 0.1~20 ppm, and auxiliary agent is product bisphosphate, and content is 0.1~1 ppm；
Wherein, toluene oxidation reaction can carry out in one or more reactors, but preferably be carried out in a reactor, this
A little reactors can be serial or parallel；
（2）Epoxidation of propylene unit
By propylene and step（1）Obtained oxidation liquid is contacted in epoxidation reaction kettle, is deposited in epoxidation catalyst
Epoxidation reaction is carried out under conditions, generates the reaction solution for mainly containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene；
Wherein, the molar ratio of propylene and benzyl hydrogen peroxide is (1~10):1, preferably (1~5):1, the pressure of epoxidation reaction
For 0.1~5 MPa, preferably 0.1~2.5 MPa, temperature is 25~200 oC, preferably 35~100 oC, the residence time is 15~
90 min；
Wherein, epoxidation reaction carries out in the presence of alkalinity additive, and alkalinity additive is alkaline metal oxide, liquefied ammonia, ammonia
One or more of water, ammonia, ammonium carbonate, organic amine, 1~10000 ppm of the mass concentration of alkalinity additive；
Wherein, propylene ring oxidation reaction can carry out in one or more reactors, these reactors can be series winding or simultaneously
Connection, preferably carries out in multiple tandem reactors；
Wherein, the main reaction formula of epoxidation reaction is such as（A）Formula：
C6H5-CH2-OOH+CH3CH=CH2→C6H5-CH2-OH+CH3CH(O)CH2（A）
Wherein, reactor used in epoxidation reaction is slurry bed system or fixed bed, preferably fixed bed；
（3）De- light component unit
By step（2）Obtained reaction solution carries out de- light processing in lightness-removing column, and tower top obtains the mixing of propylene and propylene oxide
Object, bottom of tower obtain mainly containing the mixed solution of benzaldehyde, benzyl alcohol and toluene；
Wherein, lightness-removing column tower top temperature is -40~100 oC, and preferably 15~80 oC, column bottom temperature is 25~121 oC, preferably
40~100 oC, pressure are 0.1~5.0 MPa, preferably 0.1~2.5 MPa；
（4）De- propylene units
By step（3）The mixture of obtained propylene and propylene oxide carries out de- propylene processing in propylene separation tower, and tower top obtains
To propylene, and it is collected or the propylene is back to step（2）In epoxidation of propylene unit ring is continued to participate in as raw material
Oxidation reaction, bottom of tower obtain propylene oxide solution；
Wherein, propylene separation column overhead temperatures are -40~100 oC, and preferably 25~60 oC, column bottom temperature is 25~150 oC,
It is preferred that 50~150 oC, pressure is 0.1~5.0 MPa, preferably 0.1~2.0 MPa；
（5）De- propylene oxide units
By step（4）Obtained propylene oxide solution carries out decylization Ethylene Oxide processing in propylene oxide knockout tower, and tower top obtains
Propylene oxide crude product, bottom of tower obtain containing water impurity；
Wherein, propylene oxide separation column overhead temperatures are 0~100 oC, and preferably 25~80 oC, column bottom temperature is 50~150 o
C, preferably 60~150 oC, pressure are 0.1~5.0 MPa, preferably 0.1~2.0 MPa；
（6）Propylene oxide refined unit
By step（5）Obtained propylene oxide crude product is refined in propylene oxide extractive distillation column, and tower top obtains epoxy third
Alkane product；
Wherein, propylene oxide extracting rectifying column overhead temperatures be 0~100 oC, preferably 30~80 oC, column bottom temperature be 50~
150 oC, preferably 60~110 oC, pressure are 0.1~5.0 MPa, and preferably 0.1~0.5 MPa, extractant used is C3-C10
One or more of hydrocarbon and process water, selection process water；
Wherein, extractant feed mouth can be in the middle part of tower or tower top, preferred tower top；
（7）Piptonychia benzene unit
By step（3）The obtained mixed solution for mainly containing benzaldehyde, benzyl alcohol and toluene is taken off in toluene knockout tower
Toluene processing, tower top obtains toluene, and is collected or the toluene is back to step（1）As original in toluene oxidation unit
Material continues to participate in oxidation reaction, and bottom of tower obtains mainly containing the toluene derivative of benzaldehyde and benzyl alcohol；
Wherein, toluene detaches 100~180 oC of column overhead temperatures, preferably 100~130 oC, and column bottom temperature is 120~250 oC,
It is preferred that 130~200 oC, pressure is 0.1~0.5 MPa, preferably 0.1~0.5 MPa.
Pressure in the present invention each means absolute pressure, reaction unit used, such as tower and sets unless otherwise instructed
It is standby, it is common, no particular/special requirement.
What the present invention obtained has the beneficial effect that：
The present invention is on the basis of traditional toluene oxidation and epoxidation of propylene technology, and the one kind developed prepares epoxy by toluene
The method of propane.The benzyl hydrogen peroxide that the present invention is generated using toluene oxidation provides peroxide, propylene mistake as epoxidation of propylene
Conversion ratio in oxidation reaction is more than 99.0%, and the yield of propylene oxide is more than 95%, and the purity of propylene oxide is more than 99.5%.This
Invention has production cost low, and safe, low energy consumption, and technological process is short, and operating cost is low, and equipment investment is low, environmentally protective
The features such as.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific implementation mode
Following embodiment is for illustrating the present invention., it is emphasized that these embodiments are served only for making furtherly the present invention
It is bright, and should not be construed as limiting the scope of the invention.
A kind of method preparing propylene oxide by toluene of embodiment 1, includes the following steps：
（1）Toluene oxidation unit
Toluene is pre-processed to 1.4 MPa of pressure, 170 oC of temperature, air pretreatment to 1.4 MPa, is added after 160 oC of temperature
In oxidizing reactor, it is 2 to control the molar ratio of oxygen and toluene in air:1, in 2ppm oxidation catalysts cobalt naphthenate, 2ppm
Under the synergistic effect of initiator benzyl hydrogen peroxide and 0.3ppm auxiliary agents product bisphosphate, with the oxygen in air oxygen occurs for toluene
Change reaction, in 160 oC, for pressure in 1.3 MPa, the residence time is 45 min, generates main peroxide containing benzyl for reaction temperature control
Change the oxidation liquid of hydrogen, benzyl alcohol, benzaldehyde and toluene；
（2）Epoxidation of propylene unit
By propylene and step（1）The oxidation liquid obtained in toluene oxidation unit is contacted in epoxidation reaction kettle, control
The molar ratio of propylene processed and benzyl hydrogen peroxide is 2.5:1, epoxidation reaction is carried out under epoxidation catalyst existence condition, instead
It is 40 oC to answer temperature, and reaction pressure is 1.8 MPa, residence time 40min, and the acid-base value of reaction, ammonium hydroxide are adjusted using ammonium hydroxide
The mass concentration of additive amount is 5 ppm, generates the reaction for mainly containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene
Liquid；
Wherein, propylene ring oxidation reaction carries out in two concatenated fixed bed epoxidation reaction kettles；
（3）De- light component unit
By step（2）The reaction solution obtained in epoxidation of propylene unit carries out de- light processing in lightness-removing column,
Lightness-removing column tower top temperature is 65 oC, and column bottom temperature is 85 oC, and pressure is 0.1 MPa, and tower top obtains propylene and epoxy third
The mixture of alkane, bottom of tower obtain mainly containing the mixed solution of benzaldehyde, benzyl alcohol and toluene；
（4）De- propylene units
By step（3）The mixture of the propylene and propylene oxide that are obtained in de- light component unit carries out de- third in propylene separation tower
Alkene processing, propylene separation column overhead temperatures are 35oC, and column bottom temperature is 60 oC, and pressure is 0.1 MPa, and tower top obtains propylene, and
It is collected or the propylene is back to step（2）Epoxidation reaction is continued to participate in as raw material in epoxidation of propylene unit,
Bottom of tower obtains propylene oxide solution；
（5）De- propylene oxide units
By step（4）The propylene oxide solution obtained in de- propylene units carries out in propylene oxide knockout tower at decylization Ethylene Oxide
Reason, it is 35 oC that propylene oxide, which detaches column overhead temperatures, and column bottom temperature is 75 oC, and pressure is 0.2 MPa；Tower top obtains epoxy third
Alkane crude product, bottom of tower obtain containing water impurity；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product obtained in de- propylene oxide units carries out essence in propylene oxide extractive distillation column
System, propylene oxide extracting rectifying column overhead temperatures are 34 oC, and column bottom temperature is 95 oC, and pressure 0.2MPa, extractant is work
Skill water, tower top obtain product propylene；
Wherein, extractant feed mouth is on tower top；
（7）Piptonychia benzene unit
By step（3）The mixed solution for mainly containing benzaldehyde, benzyl alcohol and toluene obtained in de- light component unit is in toluene
Piptonychia benzene processing is carried out in knockout tower, it is 120 oC that toluene, which detaches column overhead temperatures, and column bottom temperature is 165 oC, pressure 0.15
MPa, tower top obtains toluene, and is collected or the toluene is back to step（1）In toluene oxidation unit as raw material after
Continuous to participate in oxidation reaction, bottom of tower obtains mainly containing the toluene derivative of benzaldehyde and benzyl alcohol；
Pressure in the present embodiment, each means absolute pressure unless otherwise instructed.
A kind of method preparing propylene oxide by toluene of embodiment 2, includes the following steps：
（1）Toluene oxidation unit
Toluene is pre-processed to 1.5 MPa of pressure, 170 oC of temperature, air pretreatment to 1.5 MPa, is added after 170 oC of temperature
In oxidizing reactor, it is 3 to control the molar ratio of oxygen and toluene in air:1, in 2ppm oxidation catalysts cobalt naphthenate, 2ppm
Under the synergistic effect of initiator benzyl hydrogen peroxide and 0.3ppm auxiliary agents product bisphosphate, with the oxygen in air oxygen occurs for toluene
Change reaction, reaction temperature control generates main peroxide containing benzyl in 170 oC, pressure in 1.4 MPa, residence time 50min
Change the oxidation liquid of hydrogen, benzyl alcohol, benzaldehyde and toluene；
（2）Epoxidation of propylene unit
By propylene and step（1）The oxidation liquid obtained in toluene oxidation unit is contacted in epoxidation reaction kettle, control
The molar ratio of propylene processed and benzyl hydrogen peroxide is 3:1, epoxidation reaction is carried out under epoxidation catalyst existence condition, is reacted
Temperature is 42 oC, and reaction pressure is 1.9 MPa, residence time 45min, the acid-base value of reaction is adjusted using ammonium hydroxide, ammonium hydroxide adds
The mass concentration of dosage is 5 ppm, generates the reaction solution for mainly containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene；
Wherein, propylene ring oxidation reaction carries out in two concatenated fixed bed epoxidation reaction kettles；
（3）De- light component unit
By step（2）The reaction solution obtained in epoxidation of propylene unit carries out de- light processing in lightness-removing column,
Lightness-removing column tower top temperature is 67 oC, and column bottom temperature is 88 oC, and pressure is 0.1 MPa, and tower top obtains propylene and epoxy third
The mixture of alkane, bottom of tower obtain mainly containing the mixed solution of benzaldehyde, benzyl alcohol and toluene；
（4）De- propylene units
By step（3）The mixture of the propylene and propylene oxide that are obtained in de- light component unit carries out de- third in propylene separation tower
Alkene processing, propylene separation column overhead temperatures are 30oC, and column bottom temperature is 65 oC, and pressure is 0.1 MPa, and tower top obtains propylene, and
It is collected or the propylene is back to step（2）Epoxidation reaction is continued to participate in as raw material in epoxidation of propylene unit,
Bottom of tower obtains propylene oxide solution；
（5）De- propylene oxide units
By step（4）The propylene oxide solution obtained in de- propylene units carries out in propylene oxide knockout tower at decylization Ethylene Oxide
Reason, it is 40 oC that propylene oxide, which detaches column overhead temperatures, and column bottom temperature is 80 oC, and pressure is 0.2 MPa；Tower top obtains epoxy third
Alkane crude product, bottom of tower obtain containing water impurity；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product obtained in de- propylene oxide units carries out essence in propylene oxide extractive distillation column
System, propylene oxide extracting rectifying column overhead temperatures are 34 oC, and column bottom temperature is 95 oC, and pressure 0.2MPa, extractant is work
Skill water, tower top obtain product propylene；
Wherein, extractant feed mouth is on tower top；
（7）Piptonychia benzene unit
By step（3）The mixed solution for mainly containing benzaldehyde, benzyl alcohol and toluene obtained in de- light component unit is in toluene
Piptonychia benzene processing is carried out in knockout tower, it is 130 oC that toluene, which detaches column overhead temperatures, and column bottom temperature is 200 oC, pressure 0.15
MPa, tower top obtain toluene, and are collected or the toluene is back to step（1）In toluene oxidation unit as raw material after
Continuous to participate in oxidation reaction, bottom of tower obtains mainly containing the toluene derivative of benzaldehyde and benzyl alcohol；
Pressure in the present embodiment, each means absolute pressure unless otherwise instructed.
A kind of method preparing propylene oxide by toluene of embodiment 3, includes the following steps：
（1）Toluene oxidation unit
Toluene is pre-processed to 1.6 MPa of pressure, 150 oC of temperature, air pretreatment to 1.6 MPa, is added after 180 oC of temperature
In oxidizing reactor, it is 4 to control the molar ratio of oxygen and toluene in air:1, in 2ppm oxidation catalysts cobalt naphthenate, 2ppm
Under the synergistic effect of initiator benzyl hydrogen peroxide and 0.3ppm auxiliary agents product bisphosphate, with the oxygen in air oxygen occurs for toluene
Change reaction, reaction temperature control generates main peroxidating containing benzyl in 180 oC, pressure in 1.5MPa, residence time 60min
The oxidation liquid of hydrogen, benzyl alcohol, benzaldehyde and toluene；
（2）Epoxidation of propylene unit
By propylene and step（1）The oxidation liquid obtained in toluene oxidation unit is contacted in epoxidation reaction kettle, control
The molar ratio of propylene processed and benzyl hydrogen peroxide is 3.5:1, epoxidation reaction is carried out under epoxidation catalyst existence condition, instead
It is 45 oC, reaction pressure 2.3MPa, residence time 50min to answer temperature, and the acid-base value of reaction, ammonium hydroxide are adjusted using ammonium hydroxide
The mass concentration of additive amount is 6ppm, generates the reaction solution for mainly containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene；
Wherein, propylene ring oxidation reaction carries out in two concatenated fixed bed epoxidation reaction kettles；
（3）De- light component unit
By step（2）The reaction solution obtained in epoxidation of propylene unit carries out de- light processing in lightness-removing column,
Lightness-removing column tower top temperature is 60oC, column bottom temperature 88oC, pressure 2.3MPa, and tower top obtains propylene and propylene oxide
Mixture, bottom of tower obtain mainly containing the mixed solution of benzaldehyde, benzyl alcohol and toluene；
（4）De- propylene units
By step（3）The mixture of the propylene and propylene oxide that are obtained in de- light component unit carries out de- third in propylene separation tower
Alkene processing, propylene separation column overhead temperatures are 30oC, and column bottom temperature is 110 oC, pressure 2.2MPa, and tower top obtains propylene, and
It is collected or the propylene is back to step（2）Epoxidation reaction is continued to participate in as raw material in epoxidation of propylene unit,
Bottom of tower obtains propylene oxide solution；
（5）De- propylene oxide units
By step（4）The propylene oxide solution obtained in de- propylene units carries out in propylene oxide knockout tower at decylization Ethylene Oxide
Reason, it is 60 oC that propylene oxide, which detaches column overhead temperatures, and column bottom temperature is 130 oC, pressure 2.0MPa；Tower top obtains epoxy third
Alkane crude product, bottom of tower obtain containing water impurity；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product obtained in de- propylene oxide units carries out essence in propylene oxide extractive distillation column
System, propylene oxide extracting rectifying column overhead temperatures are 34 oC, and column bottom temperature is 95 oC, and pressure 0.2MPa, extractant is work
Skill water, tower top obtain product propylene；
Wherein, extractant feed mouth is on tower top；
（7）Piptonychia benzene unit
By step（3）The mixed solution for mainly containing benzaldehyde, benzyl alcohol and toluene obtained in de- light component unit is in toluene
Piptonychia benzene processing is carried out in knockout tower, it is 125 oC that toluene, which detaches column overhead temperatures, and column bottom temperature is 170 oC, pressure 0.14
MPa, tower top obtain toluene, and are collected or the toluene is back to step（1）In toluene oxidation unit as raw material after
Continuous to participate in oxidation reaction, bottom of tower obtains mainly containing the toluene derivative of benzaldehyde and benzyl alcohol；Pressure in the present embodiment, such as
No special instruction each means absolute pressure.
Claims (10)
1. a kind of method that toluene conjugated oxidation prepares propylene oxide, it is characterised in that include the following steps：
（1）Toluene oxidation unit
Toluene is added in oxidizing reactor after pretreatment respectively with molecular oxygen, and in oxidation catalyst, initiator, auxiliary agent, there are items
Oxidation reaction is carried out under part, generates the oxidation liquid of mainly hydrogen peroxide containing benzyl, benzyl alcohol, benzaldehyde and toluene；
Wherein, the pressure of oxidation reaction is 0.3~2.6 MPa, and temperature is 120~250 oC, the molar ratio of molecular oxygen and toluene
For (0.1~10):1, the residence time is 30~180 min, and oxidation catalyst is in cobalt naphthenate, cobalt acetate and cobalt benzoate
One or more, content be 0.1~20 ppm, initiator is benzyl peroxide, benzaldehyde, benzyl alcohol, benzoic acid and mistake
One or more of hydrogen oxide, content are 0.1~20 ppm, and auxiliary agent is product bisphosphate, and content is 0.1~1 ppm；
（2）Epoxidation of propylene unit
By propylene and step（1）Obtained oxidation liquid is contacted in epoxidation reaction kettle, is deposited in epoxidation catalyst
Epoxidation reaction is carried out under conditions, generates the reaction solution for mainly containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene；
Wherein, the molar ratio of propylene and benzyl hydrogen peroxide is (1~10):1, the pressure of epoxidation reaction is 0.1~5 MPa,
Temperature is 25~200 oC, and the residence time is 15~90 min；
Wherein, epoxidation reaction carries out in the presence of alkalinity additive, and alkalinity additive is alkaline metal oxide, liquefied ammonia, ammonia
The mass concentration of one or more of water, ammonia, ammonium carbonate, organic amine, alkalinity additive is 1~10000ppm；
（3）De- light component unit
By step（2）Obtained reaction solution carries out de- light processing in lightness-removing column, and tower top obtains the mixing of propylene and propylene oxide
Object, bottom of tower obtain mainly containing the mixed solution of benzaldehyde, benzyl alcohol and toluene；
Wherein, lightness-removing column tower top temperature is -40~100 oC, and column bottom temperature is 25~121 oC, and pressure is 0.1~5.0 MPa；
（4）De- propylene units
By step（3）The mixture of obtained propylene and propylene oxide carries out de- propylene processing in propylene separation tower, and tower top obtains
To propylene, and it is collected or the propylene is back to step（2）In epoxidation of propylene unit ring is continued to participate in as raw material
Oxidation reaction, bottom of tower obtain propylene oxide solution；
Wherein, propylene separation column overhead temperatures are -40~100 oC, and column bottom temperature is 25~150 oC, and pressure is 0.1~5.0
MPa；
（5）De- propylene oxide units
By step（4）Obtained propylene oxide solution carries out decylization Ethylene Oxide processing in propylene oxide knockout tower, and tower top obtains
Propylene oxide crude product, bottom of tower obtain containing water impurity；
Its oxypropylene knockout tower tower top temperature is 0~100 oC, and column bottom temperature is 50~150 oC, and pressure is 0.1~5.0
MPa；
（6）Propylene oxide refined unit
By step（5）Obtained propylene oxide crude product is refined in propylene oxide extractive distillation column, and tower top obtains epoxy third
Alkane product；
Wherein, propylene oxide extracting rectifying column overhead temperatures are 0~100 oC, and column bottom temperature is 50~150 oC, pressure 0.1
~5.0 MPa, extractant used are one or more of C3-C10 hydrocarbon and process water；
（7）Piptonychia benzene unit
By step（3）The obtained mixed solution for mainly containing benzaldehyde, benzyl alcohol and toluene is taken off in toluene knockout tower
Toluene processing, tower top obtains toluene, and is collected or the toluene is back to step（1）As original in toluene oxidation unit
Material continues to participate in oxidation reaction, and bottom of tower obtains mainly containing the toluene derivative of benzaldehyde and benzyl alcohol；
Wherein, toluene detaches 100~180 oC of column overhead temperatures, and column bottom temperature is 120~250 oC, and pressure is 0.1~0.5
MPa。
2. according to the method described in claim 1, it is characterized in that step（1）In toluene oxidation unit, molecular oxygen exists with toluene
Before oxidizing reactor is added, it is 0.8~2.6 MPa to need respective pretreatment to pressure, and temperature is 120~250 oC.
3. according to the method described in claim 1, it is characterized in that step（1）Molecular oxygen is air in toluene oxidation unit.
4. according to the method described in claim 1, it is characterized in that step（1）Oxidizing reaction temperature is in toluene oxidation unit
130~200 oC, pressure are 0.6~1.6 MPa, and the molar ratio of molecular oxygen and toluene is (1~6):1.
5. according to the method described in claim 1, it is characterized in that step（2）Propylene and benzyl peroxide in epoxidation of propylene unit
The molar ratio for changing hydrogen is (1~5):1, epoxidation reaction temperature is 35~100 oC, and pressure is 0.1~2.5 MPa.
6. according to the method described in claim 1, it is characterized in that step（3）Lightness-removing column tower top temperature is in de- light component unit
15~80 oC, column bottom temperature are 40~100 oC, and pressure is 0.1~2.5 MPa.
7. according to the method described in claim 1, it is characterized in that step（4）Propylene separation column overhead temperatures in de- propylene units
For 25~60 oC, column bottom temperature is 50~150 oC, and pressure is 0.1~2.0 MPa.
8. according to the method described in claim 1, it is characterized in that step（5）De- propylene oxide units oxypropylene knockout tower
Tower top temperature is 25~80 oC, and column bottom temperature is 60~150 oC, and pressure is 0.1~2.0 MPa.
9. according to the method described in claim 1, it is characterized in that step（6）Extractive distillation column tower in propylene oxide refined unit
Top temperature is 30~80 oC, and column bottom temperature is 60~110 oC, and pressure is 0.1~0.5 MPa.
10. according to the method described in claim 1, it is characterized in that step（7）Toluene detaches column overhead temperature in piptonychia benzene unit
Degree is 100~130 oC, and column bottom temperature is 130~200 oC, and pressure is 0.1~0.5 MPa.
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| CN113121473A (en) * | 2021-03-11 | 2021-07-16 | 中山大学 | Method for preparing 1, 2-epoxypropane by co-oxidation of propylene/isopropylbenzene under metal catalysis |
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