CN108912071A - A kind of preparation method of propylene oxide - Google Patents
A kind of preparation method of propylene oxide Download PDFInfo
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- CN108912071A CN108912071A CN201810816776.9A CN201810816776A CN108912071A CN 108912071 A CN108912071 A CN 108912071A CN 201810816776 A CN201810816776 A CN 201810816776A CN 108912071 A CN108912071 A CN 108912071A
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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
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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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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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Abstract
The invention discloses a kind of preparation methods of propylene oxide.Using toluene, molecular oxygen, propylene as raw material, propylene oxide is prepared by high temperature reaction unit, low temperature reaction unit, de- light component unit, de- propylene units, de- propylene oxide units, propylene oxide refined unit, piptonychia benzene unit.The present invention is the improvement carried out on the basis of toluene oxidation reaction and propylene ring oxidation reaction prepare propylene oxide process.With it is existing prepare the technique of propylene oxide compared with, toluene conversion per pass is high, reaction selectivity is high, high conversion rate, and low energy consumption, and process flow is short, and operating cost is low.
Description
Technical field
The present invention relates to a kind of preparation methods of organic matter, particularly as the preparation method for being a kind of propylene oxide.
Background technique
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 produce 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 method), iso-butane hydrogen peroxide method (PO/TBA method) and cumyl hydroperoxide method (CHP method), conjugated oxidation overcomes
The disadvantages 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 it is low and environmentally protective without the generation of coproduction product, simple process, cost of investment, exist
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, becomes being total in the industry
Know.
Summary of the invention
The object of the present invention is to provide one kind using toluene and propylene as raw material, and the side of propylene oxide is prepared using conjugated oxidation
Method overcomes the deficiencies in the prior art.
The present invention solves its technical problem and adopts the technical scheme that a kind of such, preparation method of propylene oxide, packet
Include following steps：
（1）High temperature reaction unit
Toluene, molecular oxygen and propylene are added in high-temperature reactor after pretreatment, deposit in oxidation catalyst and epoxidation catalyst
In lower progress oxidation reaction and epoxidation reaction, generation mainly contains propylene oxide, propylene, benzyl hydrogen peroxide, benzyl alcohol, benzene
The pyroreaction liquid of formaldehyde and toluene；
Wherein, molecular oxygen is one or more of air, pure oxygen, oxygen-enriched air or ozone, preferably air；
Wherein, the temperature in reaction process is 90~250 oC, preferably 110~200 oC；Pressure is 0.3~2.6MPa, preferably
0.6~1.8 MPa；Molecular oxygen, propylene, toluene molar ratio be (0.1~10):(0.01~2):1, preferably (1~6):(0.05
~1):1；Residence time is 30~180 min；
Wherein, the main reaction formula of pyroreaction is（A）Formula and（B）Formula：
C6H5-CH3+O2→C6H5-CH2-OOH （A）
C6H5-CH2-OOH+CH3CH=CH2→C6H5-CH2-OH+CH3CH(O)CH2 （B）
（2）Low temperature reaction unit
Under cryogenic, in low-temp reaction device, step（1）Benzyl hydrogen peroxide and propylene in resulting pyroreaction liquid
Continuation carries out epoxidation reaction under catalysts conditions, while side reaction occurs, and generation mainly contains propylene oxide, propylene, benzene
The low-temp reaction liquid of methanol, benzaldehyde and toluene；
Wherein, the temperature of Low-temperature epoxyization reaction is 25~200 oC, preferably 35~100 oC；Pressure is 0.1~5.0 MPa,
It is preferred that 0.1~2.5 MPa；The molar ratio (1-10) of propylene and benzyl hydrogen peroxide:1, preferably (2-5):1；Residence time is 15
~90 min；
Wherein, the main reaction formula of low-temp reaction is（B）Formula；
（3）De- light component unit
By step（2）Obtained low-temp reaction liquid carries out de- light processing in lightness-removing column, and tower bottom obtains mainly containing benzaldehyde, benzene
The mixed solution of methanol and toluene, tower top obtain the mixture of propylene and propylene oxide；
Wherein, lightness-removing column tower top temperature is -40~100 oC, preferably 15~80 oC；Column bottom temperature is 25~121 oC, preferably
40~100 oC；Pressure is 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, a part of propylene collects remaining propylene as propylene separation tower phegma, or remaining propylene is back in technique
Reaction is continued to participate in as raw material, tower bottom obtains propylene oxide solution；
Wherein, propylene separation column overhead temperatures are -40~100 oC, 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 the purifying of propylene oxide in propylene oxide knockout tower, and tower top obtains
Propylene oxide crude product, tower bottom obtain aqueous and light component impurity, go biochemical treatment；
Wherein, propylene oxide separation column overhead temperatures are 0~100 oC, preferably 25~80 oC；Column bottom temperature is 50~150 o
C, preferably 60~150 oC；Pressure is 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, tower bottom are impurity；
Wherein, extracting rectifying column overhead temperatures are 0~100 oC, preferably 30~80 oC；Column bottom temperature is 50~150 oC, excellent
Select 60~110 oC；Pressure is 0.1~5.0 MPa, preferably 0.1~0.5 MPa；Extractant is in C3-C10 hydrocarbon and process water
One or more, selection process water；
（7）Piptonychia benzene unit
It will be from step（3）The obtained reaction solution for mainly containing benzaldehyde, benzyl alcohol and toluene is separated in toluene after pretreatment
Tower carries out the processing of piptonychia benzene, and tower bottom obtains mainly containing the toluene derivative solution of benzaldehyde and benzyl alcohol, and tower top obtains toluene,
A part of toluene collects residual toluene as toluene tower phegma, or by residual toluene be recycled in technique as raw material after
It is continuous to participate in reaction；
Wherein, toluene separation column overhead temperatures are 100~180 oC, preferably 100~130 oC；Column bottom temperature is 120~250 o
C, preferably 130~200 oC；Pressure is 0.1~5.0 MPaa, preferably 0.1~0.5 MPa.
The present invention, the step（1）In high temperature reaction unit, pyroreaction can be in one or more high-temperature reactors
It carries out, is preferably carried out in a high-temperature reactor；If high-temperature reactor is two and two or more, connection type is string
It is even or in parallel；The high-temperature reactor is paste state bed reactor or fixed bed reactors, preferably paste state bed reactor；
The step（2）In low temperature reaction unit, low-temp reaction can carry out in one or more low-temp reaction devices, these are low
The connection type of warm reactor be it is serial or parallel, preferably carried out in the low-temp reaction device of multiple series windings；The low-temp reaction
Device is paste state bed reactor or fixed bed reactors, preferably fixed bed reactors；
The step（1）High temperature reaction unit and step（2）Nitrogen protection is required in low temperature reaction unit；
The step（1）In high temperature reaction unit, raw material toluene, molecular oxygen, propylene and protective gas nitrogen are anti-in addition high temperature
Before answering device, needing respective pretreatment to pressure is 0.8~2.6MPa, temperature is 90~250 oC；
The step（7）In piptonychia benzene unit, extractant feed mouth is in the middle part of tower or tower top, preferred tower top；
Pressure in the present invention, each means absolute pressure unless otherwise instructed.Reaction unit used and equipment, for example, it is various
Tower, be it is common, without particular/special requirement.
What the present invention obtained has the beneficial effect that：
（1）With propylene epoxidation reaction is occurred for the benzyl hydrogen peroxide that toluene oxidation obtains at the first time by the present invention, generates ring
Ethylene Oxide effectively reduces the side reaction that benzyl hydrogen peroxide voluntarily decomposes generation；
（2）Compared with existing propylene oxide process, toluene conversion per pass is improved in the present invention；The conversion ratio of propylene is big
In 99.0%, the selectivity of propylene oxide is improved, and the yield of propylene oxide is greater than 95%；The purity of propylene oxide is greater than 99.5%；
The present invention has toluene conversion per pass height, reaction conversion ratio high, and selectivity is high, and production cost is low, highly-safe, energy consumption
The features such as low, process flow is short, and operating cost is low, and equipment investment is low, environmentally protective.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
The following examples are intended to illustrate the invention., it is emphasized that these embodiments are served only for making furtherly the present invention
It is bright, it but should not be understood as limiting the scope of the invention.
A kind of preparation method of the propylene oxide of embodiment 1, includes the following steps：
（1）High temperature reaction unit
By toluene, air, propylene before high-temperature reactor is added, respective pretreatment to pressure is 1.4 MPa, temperature is 110 o
C；
Pretreated toluene, air, propylene are added in the high-temperature reactor equipped with oxidation catalyst and epoxidation catalyst,
The molar ratio of oxygen, propylene and toluene in air is 2:0.1:1, it is 110 oC in temperature, pressure is the condition of 1.3 MPa
Under, under the action of oxidation catalyst, the oxygen in toluene and air occurs oxidation reaction and generates benzyl hydrogen peroxide, generation
Epoxidation reaction occurs under the action of epoxidation catalyst and generates propylene oxide and benzyl alcohol for benzyl hydrogen peroxide and propylene, instead
45 min of residence time is answered, the pyroreaction liquid containing target product propylene oxide and benzyl hydrogen peroxide, while by-product are obtained
Benzaldehyde, benzyl alcohol, the reaction solution containing target product propylene oxide and benzyl hydrogen peroxide continuously enter low-temp reaction
Unit；
Wherein high-temperature reactor is paste state bed reactor；
Wherein the main reaction formula of pyroreaction is（A）Formula and（B）Formula：
C6H5-CH3+O2→C6H5-CH2-OOH （A）
C6H5-CH2-OOH+CH3CH=CH2→C6H5-CH2-OH+CH3CH(O)CH2 （B）
（2）Low temperature reaction unit
In low-temp reaction device, the molar ratio 2.5 of propylene and benzyl hydrogen peroxide is controlled:1, it is 40 oC in temperature, pressure is
1.8 MPa；Under the action of epoxidation catalyst, propylene and benzyl hydrogen peroxide occur epoxidation reaction and generate Ethylene Oxide and benzene
Methanol, while side reaction occurs and generates benzaldehyde, benzyl alcohol, reaction time 30min is obtained containing propylene oxide, third
Alkene, benzyl alcohol, benzaldehyde and toluene low-temp reaction liquid；
Wherein, the main reaction formula of low-temp reaction is（B）Formula；
Wherein, low-temp reaction device is two concatenated fixed bed reactors；
（3）De- light component unit
By step（2）Low-temp reaction liquid obtained in low temperature reaction unit carries out de- light processing in lightness-removing column, and tower top temperature is
65 oC, column bottom temperature are 85 oC, and operating pressure is 0.1 MPa；Tower bottom obtains mainly containing benzaldehyde, benzyl alcohol and toluene
Mixed solution, tower top obtain the mixture of propylene and propylene oxide；
（4）De- propylene units
By step（3）The mixture of propylene obtained in de- light component unit and propylene oxide carries out de- third in propylene separation tower
Alkene processing, tower top temperature are 35 oC, and column bottom temperature is 60 oC, and operating pressure is 0.1 MPa；Tower top obtains propylene, a part
Propylene is collected remaining propylene, tower bottom obtains propylene oxide solution as propylene separation tower phegma；
（5）De- propylene oxide units
By step（4）Propylene oxide solution obtained in de- propylene units carries out the pure of propylene oxide in propylene oxide knockout tower
Change, tower top temperature is 35 oC, and column bottom temperature is 75 oC, 0.15 MPa of operating pressure；Tower top obtains propylene oxide crude product, tower bottom
Aqueous and light component impurity is obtained, biochemical treatment is gone；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product that de- propylene oxide units obtain is refined in propylene oxide extractive distillation column,
Tower top temperature is 34 oC, and column bottom temperature is 95 oC, and 0.15 MPa of operating pressure, extractant is process water；Tower top obtains epoxy
Bromopropane product, tower bottom are impurity；
（7）Piptonychia benzene unit
It will be from step（3）The reaction solution that benzaldehyde, benzyl alcohol and toluene are mainly contained obtained in de- light component unit is located in advance
The processing of piptonychia benzene is carried out in toluene knockout tower after reason, tower top temperature is 125 oC, and column bottom temperature is 165 oC, and operating pressure is
0.15 MPa；Tower bottom obtains mainly containing the mixed solution of benzaldehyde and benzyl alcohol, and tower top obtains toluene, a part of toluene conduct
Toluene tower phegma, residual toluene is collected；
Wherein extractant feed mouth is on tower top；
In the present embodiment, step（1）High temperature reaction unit and step（2）Nitrogen protection is required in low temperature reaction unit；
Pressure in the present embodiment, each means absolute pressure unless otherwise instructed.
A kind of preparation method of the propylene oxide of embodiment 2, includes the following steps：
（1）High temperature reaction unit
By toluene, air, propylene before high-temperature reactor is added, respective pretreatment to pressure is 1.5 MPa, temperature is 120 o
C；
Pretreated toluene, air, propylene are added in the high-temperature reactor equipped with oxidation catalyst and epoxidation catalyst,
The molar ratio of oxygen, propylene and toluene in air is 3:0.2:1, it is 120 oC in temperature, pressure is the condition of 1.5 MPa
Under, under the action of oxidation catalyst, the oxygen in toluene and air occurs oxidation reaction and generates benzyl hydrogen peroxide, generation
Epoxidation reaction occurs under the action of epoxidation catalyst and generates propylene oxide and benzyl alcohol for benzyl hydrogen peroxide and propylene, instead
50 min of residence time is answered, the pyroreaction liquid containing target product propylene oxide and benzyl hydrogen peroxide, while by-product are obtained
Benzaldehyde, benzyl alcohol, the reaction solution containing target product propylene oxide and benzyl hydrogen peroxide continuously enter low-temp reaction
Unit；
Wherein high-temperature reactor is paste state bed reactor；
Wherein the main reaction formula of pyroreaction is（A）Formula and（B）Formula：
C6H5-CH3+O2→C6H5-CH2-OOH （A）
C6H5-CH2-OOH+CH3CH=CH2→C6H5-CH2-OH+CH3CH(O)CH2 （B）
（2）Low temperature reaction unit
In low-temp reaction device, the molar ratio 3 of propylene and benzyl hydrogen peroxide is controlled:1, it is 42 oC in temperature, pressure is
1.9MPa；Under the action of epoxidation catalyst, propylene and benzyl hydrogen peroxide occur epoxidation reaction and generate Ethylene Oxide and benzene
Methanol, while side reaction occurs and generates benzaldehyde, benzyl alcohol, reaction time is 35 min, is obtained containing propylene oxide, third
Alkene, benzyl alcohol, benzaldehyde and toluene low-temp reaction liquid；
Wherein, the main reaction formula of low-temp reaction is（B）Formula；
Wherein, low-temp reaction device is two concatenated fixed bed reactors；
（3）De- light component unit
By step（2）Low-temp reaction liquid obtained in low temperature reaction unit carries out de- light processing in lightness-removing column, and tower top temperature is
67oC, column bottom temperature are 88 oC, and operating pressure is 0.1 MPa；Tower bottom obtains mainly containing benzaldehyde, benzyl alcohol and toluene
Mixed solution, tower top obtain the mixture of propylene and propylene oxide；
（4）De- propylene units
By step（3）The mixture of propylene obtained in de- light component unit and propylene oxide carries out de- third in propylene separation tower
Alkene processing, tower top temperature are 30 oC, and column bottom temperature is 65 oC, and operating pressure is 0.1 MPa；Tower top obtains propylene, a part
Remaining propylene is back in technique as propylene separation tower phegma and continues to participate in reaction as raw material, tower bottom obtains by propylene
Propylene oxide solution；
（5）De- propylene oxide units
By step（4）Propylene oxide solution obtained in de- propylene units carries out the pure of propylene oxide in propylene oxide knockout tower
Change, tower top temperature is 40 oC, and column bottom temperature is 80 oC, 0.15 MPa of operating pressure；Tower top obtains propylene oxide crude product, tower bottom
Aqueous and light component impurity is obtained, biochemical treatment is gone；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product that de- propylene oxide units obtain is refined in propylene oxide extractive distillation column,
Tower top temperature is 34oC, and column bottom temperature 95oC, 0.15 MPa of operating pressure, extractant is process water；Tower top obtains epoxy third
Alkane product, tower bottom are impurity；
Wherein, extractant feed mouth is on tower top；
（7）Piptonychia benzene unit
It will be from step（3）The reaction solution that benzaldehyde, benzyl alcohol and toluene are mainly contained obtained in de- light component unit is located in advance
The processing of piptonychia benzene is carried out in toluene knockout tower after reason, tower top temperature is 130 oC, and column bottom temperature is 200 oC, and operating pressure is
0.1~0.2 MPa；Tower bottom obtains mainly containing the mixed solution of benzaldehyde and benzyl alcohol, and tower top obtains toluene, a part of toluene
As toluene tower phegma, residual toluene is recycled in technique and continues to participate in reaction as raw material；
In the present embodiment, step（1）High temperature reaction unit and step（2）Nitrogen protection is required in low temperature reaction unit；
Pressure in the present embodiment, each means absolute pressure unless otherwise instructed.
A kind of preparation method of the propylene oxide of embodiment 3, includes the following steps：
（1）High temperature reaction unit
By toluene, air, propylene before high-temperature reactor is added, respective pretreatment to pressure is 1.6MPa, temperature is 180 oC；
Pretreated toluene, air, propylene are added in the high-temperature reactor equipped with oxidation catalyst and epoxidation catalyst,
The molar ratio of oxygen, propylene and toluene in air is 4:0.3:1, it is 180 oC in temperature, pressure is the condition of 1.5 MPa
Under, under the action of oxidation catalyst, the oxygen in toluene and air occurs oxidation reaction and generates benzyl hydrogen peroxide, generation
Epoxidation reaction occurs under the action of epoxidation catalyst and generates propylene oxide and benzyl alcohol for benzyl hydrogen peroxide and propylene, instead
60 min of residence time is answered, the pyroreaction liquid containing target product propylene oxide and benzyl hydrogen peroxide, while by-product are obtained
Benzaldehyde, benzyl alcohol, the reaction solution containing target product propylene oxide and benzyl hydrogen peroxide continuously enter low-temp reaction
Unit；
Wherein high-temperature reactor is paste state bed reactor；
Wherein the main reaction formula of pyroreaction is（A）Formula and（B）Formula：
C6H5-CH3+O2→C6H5-CH2-OOH （A）
C6H5-CH2-OOH+CH3CH=CH2→C6H5-CH2-OH+CH3CH(O)CH2 （B）
（2）Low temperature reaction unit
In low-temp reaction device, the molar ratio 3.5 of propylene and benzyl hydrogen peroxide is controlled:1, it is 45oC in temperature, pressure is
2.3MPa；Under the action of epoxidation catalyst, propylene and benzyl hydrogen peroxide occur epoxidation reaction and generate Ethylene Oxide and benzene
Methanol, while side reaction occurs and generates benzaldehyde, benzyl alcohol, reaction time is 40 min, is obtained containing propylene oxide, third
Alkene, benzyl alcohol, benzaldehyde and toluene low-temp reaction liquid；
Wherein, the main reaction formula of low-temp reaction is（B）Formula；
Wherein, low-temp reaction device is two concatenated fixed bed reactors；
（3）De- light component unit
By step（2）Low-temp reaction liquid obtained in low temperature reaction unit carries out de- light processing in lightness-removing column, and tower top temperature is
60oC, column bottom temperature are 130 oC, operating pressure 2.3MPa；Tower bottom obtains mainly containing benzaldehyde, benzyl alcohol and toluene
Mixed solution, tower top obtain the mixture of propylene and propylene oxide；
（4）De- propylene units
By step（3）The mixture of propylene obtained in de- light component unit and propylene oxide carries out de- third in propylene separation tower
Alkene processing, tower top temperature are 30 oC, and column bottom temperature is 110 oC, and operating pressure is 2.2 MPa；Tower top obtains propylene, a part
Propylene is collected remaining propylene, tower bottom obtains propylene oxide solution as propylene separation tower phegma；
（5）De- propylene oxide units
By step（4）Propylene oxide solution obtained in de- propylene units carries out the pure of propylene oxide in propylene oxide knockout tower
Change, tower top temperature is 60 oC, and column bottom temperature is 130 oC, 2.0 MPa of operating pressure；Tower top obtains propylene oxide crude product, tower bottom
Aqueous and light component impurity is obtained, biochemical treatment is gone；
（6）Propylene oxide refined unit
By step（5）The propylene oxide crude product that de- propylene oxide units obtain is refined in propylene oxide extractive distillation column,
Tower top temperature is 34oC, and column bottom temperature 95oC, 0.15 MPa of operating pressure, extractant is process water；Tower top obtains epoxy third
Alkane product, tower bottom are impurity；
（7）Piptonychia benzene unit
It will be from step（3）The reaction solution that benzaldehyde, benzyl alcohol and toluene are mainly contained obtained in de- light component unit is located in advance
The processing of piptonychia benzene is carried out after reason in toluene knockout tower, tower top temperature is 125 oC, and column bottom temperature is 170 oC, and operating pressure is
0.1~0.2 MPa；Tower bottom obtains mainly containing the mixed solution of benzaldehyde and benzyl alcohol, and tower top obtains toluene, a part of toluene
As toluene tower phegma, residual toluene is recycled in technique and continues to participate in reaction as raw material.
Claims (10)
1. a kind of preparation method of propylene oxide, it is characterised in that include the following steps：
（1）High temperature reaction unit
Toluene, molecular oxygen and propylene are added in high-temperature reactor after pretreatment, deposit in oxidation catalyst and epoxidation catalyst
In lower progress oxidation reaction and epoxidation reaction, generation mainly contains propylene oxide, propylene, benzyl hydrogen peroxide, benzyl alcohol, benzene
The pyroreaction liquid of formaldehyde and toluene；
Wherein, the temperature in high-temperature reaction process is 90~250 oC, and pressure is 0.3~2.6MPa, molecular oxygen, propylene, toluene
Molar ratio be (0.1~10):(0.01~2):1, the residence time is 30~180 min；
（2）Low temperature reaction unit
Under cryogenic, in low-temp reaction device, step（1）Benzyl in pyroreaction liquid obtained in high temperature reaction unit
Hydrogen peroxide and propylene continuation carry out epoxidation reaction under the conditions of epoxidation catalyst, while side reaction occurs, and generate main
Low-temp reaction liquid containing propylene oxide, propylene, benzyl alcohol, benzaldehyde and toluene；
Wherein, the temperature of Low-temperature epoxyization reaction is 25~200 oC, and pressure is 0.1~5.0 MPa, propylene and benzyl peroxidating
The molar ratio (1-10) of hydrogen:1, the residence time is 15~90 min；
（3）De- light component unit
By step（2）Obtained low-temp reaction liquid carries out de- light processing in lightness-removing column, and tower bottom obtains mainly containing benzaldehyde, benzene
The mixed solution of methanol and toluene, tower top obtain the mixture of propylene and propylene oxide；
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, a part of propylene collects remaining propylene as propylene separation tower phegma, or remaining propylene is back in technique
Reaction is continued to participate in as raw material, tower bottom obtains 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 the purifying of propylene oxide in propylene oxide knockout tower, and tower top obtains
Propylene oxide crude product, tower bottom obtain aqueous and light component impurity, go biochemical treatment；
Wherein, propylene oxide separation column overhead temperatures be 0~100 oC, column bottom temperature be 50~150 oC, pressure be 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, tower bottom are impurity；
Wherein extracting rectifying column overhead temperatures are 0~100 oC, and column bottom temperature is 50~150 oC, and pressure is 0.1~5.0
MPa；Extractant is one of C3-C10 hydrocarbon and process water or a variety of；
（7）Piptonychia benzene unit
It will be from step（3）The obtained reaction solution for mainly containing benzaldehyde, benzyl alcohol and toluene is separated in toluene after pretreatment
Tower carries out the processing of piptonychia benzene, and tower bottom obtains mainly containing the toluene derivative solution of benzaldehyde and benzyl alcohol, and tower top obtains toluene,
A part of toluene collects residual toluene as toluene tower phegma, or by residual toluene be recycled in technique as raw material after
It is continuous to participate in reaction；
Wherein, toluene separation column overhead temperatures are 100~180 oC, and column bottom temperature is 120~250 oC, and pressure is 0.1~5.0
MPa。
2. according to the method described in claim 1, it is characterized in that step（1）High temperature reaction unit
In, molecular oxygen is air, and the temperature in high-temperature reaction process is 110~200 oC, and pressure is 0.6~1.8 MPa；Molecule
Oxygen, propylene, toluene molar ratio be (1~6):(0.05~1):1.
3. preparation method according to claim 1, it is characterised in that step（1）High temperature reaction unit and step（2）Low temperature
Nitrogen protection is required in reaction member；The pH value of reaction is adjusted using alkalinity additive.
4. according to the method described in claim 1, it is characterized in that step（1）High temperature reaction unit
In, raw material toluene, molecular oxygen, propylene and protective gas nitrogen are before being added high-temperature reactor, respective pretreatment to pressure
It is 90~250 oC for 0.8~2.6MPa, temperature.
5. according to the method described in claim 1, it is characterized in that step（2）In low temperature reaction unit, Low-temperature epoxyization reaction
Temperature be preferably 35~100 oC, pressure is 0.1~2.5 MPa, and the molar ratio of propylene and benzyl hydrogen peroxide is (2~5):
1。
6. according to the method described in claim 1, it is characterized in that step（3）In de- light component unit, lightness-removing column tower top temperature
For 15~80 oC, column bottom temperature is 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）In de- propylene units, propylene separation column overhead temperature
Degree is preferably 25~60 oC, and 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）In de- propylene oxide units, propylene oxide separation
Column overhead temperatures are 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）In propylene oxide refined unit, extractive distillation column
Tower 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）In piptonychia benzene unit, toluene separates column overhead temperature
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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| US6160137A (en) * | 1997-11-07 | 2000-12-12 | Sumitomo Chemical Company, Limited | Method for producing propylene oxide |
| CN1310698A (en) * | 1998-07-20 | 2001-08-29 | 国际壳牌研究有限公司 | Process for the preparation of styrene and propylene oxide |
| CN106699695A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Production method of propylene oxide |
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2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6160137A (en) * | 1997-11-07 | 2000-12-12 | Sumitomo Chemical Company, Limited | Method for producing propylene oxide |
| CN1310698A (en) * | 1998-07-20 | 2001-08-29 | 国际壳牌研究有限公司 | Process for the preparation of styrene and propylene oxide |
| CN106699695A (en) * | 2016-10-31 | 2017-05-24 | 中石化南京工程有限公司 | Production method of propylene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10844295B1 (en) | 2019-10-11 | 2020-11-24 | Saudi Arabian Oil Company | Systems and processes to deolefinate aromatic-rich hydrocarbon streams |
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