CN105669398B - Produce the device and method of benzaldehyde - Google Patents
Produce the device and method of benzaldehyde Download PDFInfo
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- CN105669398B CN105669398B CN201610025600.2A CN201610025600A CN105669398B CN 105669398 B CN105669398 B CN 105669398B CN 201610025600 A CN201610025600 A CN 201610025600A CN 105669398 B CN105669398 B CN 105669398B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The present invention provides a kind of device producing benzaldehyde, including：Oxidation unit is used for toluene and air successive reaction under the action of catalyst, forms tail gas and oxidation solution；The toluene flash column being connected to oxidation unit bottom；The de- high boiling tower being connected to toluene flash distillation tower bottom；With the benzaldehyde lightness-removing column being connected at the top of de- high boiling tower；And the benzaldehyde rectifying column being connected to benzaldehyde lightness-removing column bottom.The present invention also provides a kind of methods producing benzaldehyde.Successive reaction, oxidation solution flash, through a series of after distillation operation under the action of catalyst for the device and method of above-mentioned production benzaldehyde, toluene and air, and obtained benzaldehyde purity selectively can reach 15% or more up to 99.8% or more.
Description
Technical field
The present invention relates to chemical fields, more particularly to the device and method of production benzaldehyde.
Background technology
Benzaldehyde is a kind of important industrial chemicals, is at room temperature colourless liquid, has special almond scent, uses extensively
The intermediate for making synthesis medicine, fuel, fragrance, can also be used alone as fragrance.
The industrial process of benzaldehyde is mainly chlorination toluene Hydrolyze method at present, and a large amount of pollutions are generated in production process
Serious industrial wastewater contains chlorine in product, influences product quality, and production cost is high.
The a small amount of benzaldehyde of by-product during toluene oxidation benzoic acid, but benzaldehyde selects when conventional method oxidation reaction
Property it is low, recycling process for refining it is unreasonable, benzaldehyde yield is relatively low, without industrial value.
CN1296937A discloses the preparation method of a kind of benzoic acid, benzaldehyde, benzyl alcohol, by toluene in the liquid phase with
Chlorine-containing gas is aoxidized with gas in the presence of major catalyst cobalt salt or cobalt salt manganese addition salt, co-catalyst bromide and its catalyst and is made
The method of standby benzoic acid, benzaldehyde, benzyl alcohol.But this method needs to add bromide as co-catalyst, is easy to equipment
It damages.
Invention content
Based on this, it is necessary to which the problem of being directed to background technology provides a kind of safe and environment-friendly and can obtain high-purity
The device of the production benzaldehyde of benzaldehyde.
In addition, the present invention also provides a kind of methods producing benzaldehyde.
A kind of device producing benzaldehyde, including：
Oxidation unit is used for toluene and air successive reaction under the action of catalyst, forms tail gas and oxidation solution；
The toluene flash column being connected to the oxidation unit bottom obtains toluene for being flashed to the oxidation solution
Flash column tower top material and toluene flash column materials at bottom of tower；
The de- high boiling tower being connected to toluene flash distillation tower bottom, is used for the toluene flash column materials at bottom of tower rectifying,
Obtain de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower；
The benzaldehyde lightness-removing column being connected to at the top of the de- high boiling tower, is used for the de- high boiling tower tower top material rectifying,
Obtain benzaldehyde lightness-removing column tower top material and benzaldehyde lightness-removing column materials at bottom of tower；
The benzaldehyde rectifying column being connected to benzaldehyde lightness-removing column bottom, for the benzaldehyde lightness-removing column bottoms
Expect rectifying, obtains benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower.
The oxidation unit includes oxidizing tower, circulating pump and steam generator, the oxidation in one of the embodiments,
Tower is externally provided with chuck, and coil pipe is equipped in the oxidizing tower；
The bottom of the oxidizing tower passes sequentially through the circulating pump and steam generator with the oxidizing tower close to top
Side is connected to, and is exchanged heat with water for most of oxidation solution to be pumped to steam generator through cycle, is obtained steam and heat exchange
Oxidation solution afterwards, the oxidation solution after the heat exchange are back in the oxidizing tower；
The bottom of the oxidizing tower is connected to the toluene flash column, for sending oxidation solution described in small part to the first
Benzene flash column is flashed.
The top of the oxidizing tower is equipped with feed inlet and exhaust port, the feed inlet in one of the embodiments,
For being continuously passed through toluene and catalyst, the exhaust port is for the tail gas to be discharged.
The top of the toluene flash column is connected to the feed inlet in one of the embodiments, is used for the first
Benzene flash column tower top material is back in the oxidizing tower；
The top of the benzaldehyde lightness-removing column is connected to the feed inlet, is used for the benzaldehyde lightness-removing column tower top material
It is back in the oxidizing tower；
The bottom of the benzaldehyde rectifying column is connected to the feed inlet, for benzaldehyde rectifying tower bottom is exposed
It is small to be back in the oxidizing tower.
The device of the production benzaldehyde further includes multi-stage condensing device and multi-stage absorption device in one of the embodiments,
The multi-stage condensing device is connected to the exhaust port, multi-stage absorption device and feed inlet respectively.
A method of benzaldehyde is produced, is included the following steps：
By toluene and air successive reaction under the action of catalyst, tail gas and oxidation solution are formed；
The oxidation solution is flashed, toluene flash column tower top material and toluene flash column materials at bottom of tower are obtained；
To the toluene flash column materials at bottom of tower rectifying, de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower are obtained；
To the de- high boiling tower tower top material rectifying, benzaldehyde lightness-removing column tower top material and benzaldehyde lightness-removing column bottom of tower are obtained
Material；
To the benzaldehyde lightness-removing column materials at bottom of tower rectifying, benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower are obtained.
In one of the embodiments, it is described by toluene and air under the action of catalyst successive reaction the step of in, institute
The charging proportioning for stating air and toluene is 50 Nm3 ~800Nm3:1000kg, reaction time are 0.5 ~ 10 hour, reaction temperature
Degree is 130 DEG C ~ 185 DEG C, and reaction pressure is 300 kPa ~ 1000kPa.
The catalyst is the aqueous solution of cobalt benzoate, the aqueous solution of the cobalt benzoate in one of the embodiments,
The mass ratio of middle cobalt benzoate and water is 1:4 ~ 20, a concentration of 20 ppm ~ 300ppm of metal cobalt ions in the reaction system.
The oxidation solution is flashed in one of the embodiments, obtains toluene flash column tower top material and toluene
The step of flash column materials at bottom of tower is specially：
After most of oxidation solution is exchanged heat with water, the oxidation solution after obtaining steam and exchanging heat, the oxygen after the heat exchange
Change liquid and returns to the participation successive reaction；
Oxidation solution described in small part is flashed, toluene flash column tower top material and toluene flash column materials at bottom of tower are obtained.
The method of the production benzaldehyde is further comprising the steps of in one of the embodiments,：
The toluene flash column tower top material is returned and participates in the successive reaction；
The benzaldehyde lightness-removing column tower top material is returned and participates in the successive reaction；
The benzaldehyde rectifying column materials at bottom of tower is returned and participates in the successive reaction.
Successive reaction, oxidation solution pass through under the action of catalyst for the device and method of above-mentioned production benzaldehyde, toluene and air
After a series of flash distillations, distillation operation, obtained benzaldehyde purity selectively can reach 15% or more up to 99.8% or more.
In addition, the heat release under the action of catalyst of toluene and air, reaction heat pass through in chuck, coil pipe, steam generator
At least one byproduct steam, toluene flash column tower top material, benzaldehyde lightness-removing column tower top material, benzaldehyde rectifying column materials at bottom of tower
Successive reaction, energy conservation and environmental protection are participated in Deng oxidizing tower is returned.
Description of the drawings
Fig. 1 is the structural schematic diagram of the device of the production benzaldehyde of an embodiment.
Fig. 2 is the structural schematic diagram of oxidation unit in Fig. 1.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Specific implementation mode be described in detail.Many details are elaborated in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case of violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Referring to Fig. 1, the device of the production benzaldehyde of an embodiment, including it is oxidation unit 10, toluene flash column 20, de-
High boiling tower 30, benzaldehyde lightness-removing column 40 and benzaldehyde rectifying column 50.
Wherein, oxidation unit 10 is used for toluene and air successive reaction under the action of catalyst, forms tail gas and oxidation solution.
Referring to Fig. 2, in the present embodiment, oxidation unit 10 includes oxidizing tower 110, circulating pump 120 and steam generation
Device 130.
Wherein, oxidizing tower 110 is externally provided with chuck 140, is interior equipped with coil pipe 150.
The bottom of oxidizing tower 110 passes sequentially through circulating pump 120 and steam generator 130 with oxidizing tower 110 close to top
Side is connected to, and is exchanged heat for being sent most of oxidation solution to steam generator 130 and water through circulating pump 120, is obtained steam and is changed
Oxidation solution after heat, the oxidation solution after heat exchange are returned again into oxidizing tower 110.
It is appreciated that added with soft water in chuck 140, coil pipe 150 and steam generator 130, toluene and air are in catalyst
The lower exothermic heat of reaction of effect, reaction heat is by least one of chuck 140, coil pipe 150, steam generator 130 byproduct steam, instead
Heat is answered to be recycled.
In the present embodiment, the top of oxidizing tower 110 is equipped with feed inlet 112 and exhaust port 114.
Wherein, feed inlet 112 is for being continuously passed through toluene and catalyst.
Exhaust port 114 is for above-mentioned tail gas to be discharged.
Toluene flash column 20 is connected to 10 bottom of oxidation unit.Toluene flash column 20 is for dodging above-mentioned oxidation solution
It steams, obtains toluene flash column tower top material and toluene flash column materials at bottom of tower.
Specifically, the middle part of toluene flash column 20 is connected to the bottom of oxidizing tower 110, for the above-mentioned oxidation solution of small part
Flash distillation, obtains toluene flash column tower top material and toluene flash column materials at bottom of tower.
It is largely toluene in toluene flash column tower top material, in order to recycle this part toluene, toluene flash column 20
Top be connected to feed inlet 112, for toluene flash column tower top material to be back in oxidizing tower 110.
De- high boiling tower 30 is connected to the bottom of toluene flash column 20.De- high boiling tower 30 is used for above-mentioned toluene flash column bottom of tower
Material rectifying obtains de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower.
Wherein, take off and contain benzoic acid, Ergol and catalyst in high boiling tower materials at bottom of tower, for produce benzoic acid,
Ergol and recycling catalyst.
Specifically, the middle part of de- high boiling tower 30 is connected to the bottom of toluene flash column 20.
Benzaldehyde lightness-removing column 40 is connected to the top of de- high boiling tower 30.Benzaldehyde lightness-removing column 40 is used for above-mentioned de- high boiling tower
Tower top material rectifying obtains benzaldehyde lightness-removing column tower top material and benzaldehyde lightness-removing column materials at bottom of tower.
Specifically, the middle part of benzaldehyde lightness-removing column 40 is connected to the top of de- high boiling tower 30.
Wherein, it is largely toluene in benzaldehyde lightness-removing column tower top material, in order to recycle this part toluene, benzaldehyde
The top of lightness-removing column 40 is connected to feed inlet 112, for benzaldehyde lightness-removing column tower top material to be back in oxidizing tower 110.
Benzaldehyde rectifying column 50 is connected to the bottom of benzaldehyde lightness-removing column 40.Benzaldehyde rectifying column 50 is used for above-mentioned benzene first
Aldehyde lightness-removing column materials at bottom of tower rectifying, obtains benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower.
Wherein, in benzaldehyde finished product the content of benzaldehyde 99.8% or more.
In benzaldehyde rectifying column materials at bottom of tower largely be benzyl alcohol, benzoic acid, the bottom of benzaldehyde rectifying column 50 with into
Material mouth 112 is connected to, for benzaldehyde rectifying column materials at bottom of tower to be back in oxidizing tower 110.
In the present embodiment, the device of above-mentioned production benzaldehyde further includes multi-stage condensing device 60 and multi-stage absorption device
70。
Wherein, multi-stage condensing device 60 is connected to exhaust port 114, multi-stage absorption device 70 and feed inlet 112 respectively.
Specifically, multi-stage absorption device 70 is 1 ~ 4 grade of adsorbent equipment.Multi-stage condensing device 60 is 2 ~ 4 grades of condensing units.
Tail gas condenses the qualified discharge after the absorption of multi-stage absorption device 70 again through multi-stage condensing device 60.
The material condensed out through multi-stage condensing device 60 is back to through feed inlet 112 in oxidizing tower 110.
The material absorbed through multi-stage absorption device 70 is toluene and benzene, goes to detach to obtain finished product benzene and toluene.
The device of above-mentioned production benzaldehyde, toluene and air successive reaction under the action of catalyst, oxidation solution is through a series of
After flash distillation, distillation operation, obtained benzaldehyde purity selectively can reach 15% or more up to 99.8% or more.
In addition, the heat release under the action of catalyst of toluene and air, reaction heat passes through chuck 140, coil pipe 150, steam generation
At least one of device 130 byproduct steam, toluene flash column tower top material, benzaldehyde lightness-removing column tower top material, benzaldehyde rectifying
Tower materials at bottom of tower etc. returns to oxidizing tower and participates in successive reaction, energy conservation and environmental protection.
A kind of method of continuous production benzaldehyde, includes the following steps：
S110, by toluene and air successive reaction under the action of catalyst, form tail gas and oxidation solution.
Wherein, the charging proportioning of air and toluene is 50 Nm3 ~800Nm3:1000kg.Preferably, air and toluene into
Material proportioning is 150 Nm3~250 Nm3:1000kg。
Reaction time is 0.5 ~ 10 hour.Preferably, reaction time is 4 ~ 5 hours.
Reaction temperature is 130 DEG C ~ 185 DEG C.Preferably, reaction temperature is 145 DEG C ~ 155 DEG C.
Reaction absolute pressure is 300 kPa ~ 1000kPa.Preferably, reaction absolute pressure is 600 kPa ~ 800kPa.
Catalyst is the aqueous solution of cobalt benzoate.
Wherein, the mass ratio of cobalt benzoate and water is 1 in cobalt benzoate aqueous solution:4~20.Metal cobalt ions is in reactant
A concentration of 20 ~ 300ppm in system.
Preferably, a concentration of 40 ~ 100ppm of metal cobalt ions in the reaction system, benzoic acid in cobalt benzoate aqueous solution
The mass ratio of cobalt and water is 1:8~15.
Specifically, toluene, catalyst are from oxidation tower top continuous feed, air is from the continuous feed of oxidizing tower bottom, toluene and sky
Gas successive reaction under the action of catalyst forms tail gas and oxidation solution.
In the present embodiment, tail gas qualified discharge after multi-stage condensing, multi-stage absorption.
By toluene, catalyst from oxidation tower top continuous feed, come into full contact with from the air of oxidizing tower bottom continuous feed, instead
It should be easier to make for, the consumption of catalyst can be reduced.
S120, above-mentioned oxidation solution is flashed, obtains toluene flash column tower top material and toluene flash column materials at bottom of tower.
Wherein, after most of above-mentioned oxidation solution being exchanged heat with water, the oxidation solution after obtaining steam and exchanging heat, the oxygen after heat exchange
Change liquid and return to oxidizing tower participation successive reaction, reaction heat most of in this way stays in oxidizing tower, can generate more steam.
Small part oxidation solution is flashed, toluene flash column tower top material and toluene flash column materials at bottom of tower are obtained.
It is flashed in the middle part of toluene flash column specifically, small part oxidation solution is continuously entered, obtains toluene flash column
Tower top material and toluene flash column materials at bottom of tower.
Wherein, the absolute pressure of toluene flash column be 100 kpa ~ 120kpa, toluene flash column overhead temperatures be 102 DEG C ~
150℃.Preferably, the absolute pressure of toluene flash column be 105 kpa ~ 110kpa, toluene flash column overhead temperatures be 110 DEG C ~
130℃。
Into in the oxidation solution of toluene flash column, benzoic acid content is 8 ~ 16%, and benzaldehyde content is 2 ~ 4%.
In the present embodiment, toluene flash column tower top material returns to oxidizing tower and participates in successive reaction, toluene flash column tower
Substrate material, which enters, to be taken off in the middle part of high boiling tower.
S130, to above-mentioned toluene flash column materials at bottom of tower rectifying, obtain de- high boiling tower tower top material and de- high boiling tower bottom of tower
Material.
Specifically, toluene flash column materials at bottom of tower, which enters, takes off rectifying in the middle part of high boiling tower, obtain de- high boiling tower tower top material and
De- high boiling tower materials at bottom of tower.
Wherein, it is 10 kPa ~ 40kPa to take off high boiling tower absolute pressure of top of the tower, and tower top temperature is 130 DEG C ~ 165 DEG C, preferably
, it is 20 kPa ~ 30kPa to take off high boiling tower absolute pressure of top of the tower, and it is 135 DEG C ~ 156 DEG C to take off height boiling tower top temperature.
Contain benzoic acid, Ergol and catalyst in de- high boiling tower materials at bottom of tower, subsequent handling can be entered and produced
Benzoic acid, Ergol and recycling catalyst.
De- high boiling tower tower top material enters in the middle part of benzaldehyde lightness-removing column.
S140, to above-mentioned de- high boiling tower tower top material rectifying, obtain benzaldehyde lightness-removing column tower top material and benzaldehyde be de- light
Tower materials at bottom of tower.
Specifically, above-mentioned de- high boiling tower tower top material enters rectifying in the middle part of benzaldehyde lightness-removing column, benzaldehyde lightness-removing column is obtained
Tower top material and benzaldehyde lightness-removing column materials at bottom of tower.
Wherein, benzaldehyde lightness-removing column absolute pressure of top of the tower is 15 kPa ~ 60kPa, and tower top temperature is 54 DEG C ~ 110 DEG C, excellent
Choosing, benzaldehyde lightness-removing column absolute pressure of top of the tower is 20 kPa ~ 40kPa, and tower top temperature is 65 DEG C ~ 90 DEG C.
Benzaldehyde lightness-removing column tower top material returns to oxidizing tower and participates in successive reaction.
Benzaldehyde lightness-removing column materials at bottom of tower enters in the middle part of benzaldehyde rectifying column.
S150, to above-mentioned benzaldehyde lightness-removing column materials at bottom of tower rectifying, obtain benzaldehyde finished product and benzaldehyde rectifying tower bottom
Material.
Specifically, benzaldehyde lightness-removing column materials at bottom of tower enters rectifying in the middle part of benzaldehyde rectifying column, obtain benzaldehyde finished product and
Benzaldehyde rectifying column materials at bottom of tower.
Wherein, benzaldehyde rectifying column tower top absolute pressure is 15 kPa ~ 50kPa, and tower top temperature is 113.5 DEG C ~ 150 DEG C,
Preferably, benzaldehyde rectifying column tower top absolute pressure is 20 kPa ~ 40kPa, and tower top temperature is 122.7 DEG C ~ 144.3 DEG C.
The mass content of benzaldehyde is 99.8% or more in benzaldehyde finished product.
Benzaldehyde rectifying column materials at bottom of tower returns to oxidizing tower and participates in successive reaction.
The method of above-mentioned production benzaldehyde, toluene and air successive reaction under the action of catalyst, it is not necessary that bromide is added
It is safe and environment-friendly as co-catalyst.For oxidation solution after a series of flash distillations, distillation operation, obtained benzaldehyde purity is reachable
99.8% or more, it selectively can reach 15% or more.
It is specific embodiment below.
Embodiment 1
Toluene with 46000kg/h, cobalt benzoate with 14kg/h, water with the speed of 112kg/h from oxidation tower top continuous feed,
Air is with 11500Nm3The speed of/h is from the continuous feed of oxidizing tower bottom, toluene and air successive reaction under the effect of the catalyst,
Form tail gas and oxidation solution.Wherein, reaction temperature is 145 DEG C, reaction pressure 700kPa, and mean residence time is 5 hours.
Tail gas qualified discharge after multi-stage condensing, multi-stage absorption, most of above-mentioned oxidation solution are pumped to steam hair by recycling
Raw device obtains the oxidation solution after steam and heat exchange, the oxidation solution after heat exchange returns to oxidizing tower, and the reaction was continued with after water heat exchange.
The above-mentioned oxidation solution of small part continuously enters to be flashed in the middle part of toluene flash column, obtains toluene flash column overhead materials
Material and toluene flash column materials at bottom of tower.Wherein, toluene flashes absolute pressure of top of the tower 108kpa, and top temperature is 115 DEG C, into toluene
In the oxidation solution of flash column, benzoic acid content 15%, benzaldehyde content is 3%.
Toluene flash column tower top material returns to oxidizing tower, and the reaction was continued, and toluene flash column materials at bottom of tower, which enters, to be taken off in high boiling tower
Portion's rectifying obtains de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower.Wherein, taking off high boiling tower absolute pressure of top of the tower is
20kPa, tower top temperature are 135 DEG C.
De- high boiling tower tower top material enters rectifying in the middle part of benzaldehyde lightness-removing column, obtains benzaldehyde lightness-removing column tower top material and benzene
Formaldehyde lightness-removing column materials at bottom of tower.Wherein, benzaldehyde lightness-removing column absolute pressure of top of the tower is 30kPa, and tower top temperature is 78 DEG C.
Benzaldehyde lightness-removing column tower top material returns to oxidizing tower, and the reaction was continued, and benzaldehyde lightness-removing column materials at bottom of tower enters benzaldehyde
Rectifying in the middle part of rectifying column, obtains the benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower of 1200kg/h.Wherein, benzaldehyde rectifying
Column overhead absolute pressure is 30kPa, and tower top temperature is 133.2 DEG C.
Benzaldehyde rectifying column materials at bottom of tower returns to oxidizing tower, and the reaction was continued, and the purity of benzaldehyde finished product is 99.92%.
Embodiment 2
Toluene with 57500kg/h, cobalt benzoate with 7kg/h, water with the speed of 105kg/h from oxidation tower top continuous feed,
Air is with 8625Nm3The speed of/h successive reaction under the action of cobalt benzoate from the continuous feed of oxidizing tower bottom, toluene and air,
Form tail gas and oxidation solution.Wherein, reaction temperature is 155 DEG C, reaction pressure 800kPa, and mean residence time is 4 hours.
Tail gas qualified discharge after multi-stage condensing, multi-stage absorption, most of above-mentioned oxidation solution are pumped to steam hair by recycling
Raw device obtains the oxidation solution after steam and heat exchange, the oxidation solution after heat exchange returns to oxidizing tower, and the reaction was continued with after water heat exchange.
The above-mentioned oxidation solution of small part continuously enters to be flashed in the middle part of toluene flash column, obtains toluene flash column overhead materials
Material and toluene flash column materials at bottom of tower.Wherein, toluene flashes absolute pressure of top of the tower 110kpa, and top temperature is 130 DEG C, into first
In the oxidation solution of benzene flash column, benzoic acid content 9%, benzaldehyde content is 2%.
Toluene flash column tower top material returns to oxidizing tower, and the reaction was continued, and toluene flash column materials at bottom of tower, which enters, to be taken off in high boiling tower
Portion's rectifying obtains de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower.Wherein, taking off high boiling tower absolute pressure of top of the tower is
30kPa, tower top temperature are 156 DEG C.
De- high boiling tower tower top material enters rectifying in the middle part of benzaldehyde lightness-removing column, obtains benzaldehyde lightness-removing column tower top material and benzene
Formaldehyde lightness-removing column materials at bottom of tower.Wherein, benzaldehyde lightness-removing column absolute pressure of top of the tower is 20kPa, and tower top temperature is 65 DEG C.
Benzaldehyde lightness-removing column tower top material returns to oxidizing tower, and the reaction was continued, and benzaldehyde lightness-removing column materials at bottom of tower enters benzaldehyde
Rectifying in the middle part of rectifying column, obtains the benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower of 1000kg/h.Wherein, benzaldehyde rectifying
Column overhead absolute pressure is 20kPa, and tower top temperature is 122.7 DEG C.
Benzaldehyde rectifying column materials at bottom of tower returns to oxidizing tower, and the reaction was continued, and the purity of benzaldehyde finished product is 99.86%.
Embodiment 3
Toluene with 51100kg/h, cobalt benzoate with the speed of 15kg/h from oxidation tower top continuous feed, air with
10200Nm3The speed of/h successive reaction under the action of cobalt benzoate from the continuous feed of oxidizing tower bottom, toluene and air is formed
Tail gas and oxidation solution.Wherein, reaction temperature is 150 DEG C, reaction pressure 600kPa, and mean residence time is 4.5 hours.
Tail gas qualified discharge after multi-stage condensing, multi-stage absorption, most of above-mentioned oxidation solution are pumped to steam hair by recycling
Raw device obtains the oxidation solution after steam and heat exchange, the oxidation solution after heat exchange returns to oxidizing tower, and the reaction was continued with after water heat exchange.
The above-mentioned oxidation solution of small part continuously enters to be flashed in the middle part of toluene flash column, obtains toluene flash column overhead materials
Material and toluene flash column materials at bottom of tower.Wherein, toluene flashes absolute pressure of top of the tower 105kpa, and top temperature is 110 DEG C, into toluene
In the oxidation solution of flash column, benzoic acid content 12%, benzaldehyde content is 2.8%.
Toluene flash column tower top material returns to oxidizing tower, and the reaction was continued, and toluene flash column materials at bottom of tower, which enters, to be taken off in high boiling tower
Portion's rectifying obtains de- high boiling tower tower top material and de- high boiling tower materials at bottom of tower.Wherein, taking off high boiling tower absolute pressure of top of the tower is
25kPa, tower top temperature are 145 DEG C.
De- high boiling tower tower top material enters rectifying in the middle part of benzaldehyde lightness-removing column, obtains benzaldehyde lightness-removing column tower top material and benzene
Formaldehyde lightness-removing column materials at bottom of tower.Wherein, benzaldehyde lightness-removing column absolute pressure of top of the tower is 40kPa, and tower top temperature is 90 DEG C.
Benzaldehyde lightness-removing column tower top material returns to oxidizing tower, and the reaction was continued, and benzaldehyde lightness-removing column materials at bottom of tower enters benzaldehyde
Rectifying in the middle part of rectifying column, obtains the benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower of 1290kg/h.Wherein, benzaldehyde rectifying
Column overhead absolute pressure is 40kPa, and tower top temperature is 144.3 DEG C.
Benzaldehyde rectifying column materials at bottom of tower returns to oxidizing tower, and the reaction was continued, and the purity of benzaldehyde finished product is 99.92%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (3)
1. a kind of device producing benzaldehyde, which is characterized in that including：
Oxidation unit is used for toluene and air successive reaction under the action of catalyst, forms tail gas and oxidation solution；
The toluene flash column being connected to the oxidation unit bottom obtains toluene flash distillation for being flashed to the oxidation solution
Column overhead material and toluene flash column materials at bottom of tower；
The de- high boiling tower being connected to toluene flash distillation tower bottom, for the toluene flash column materials at bottom of tower rectifying, obtaining
De- high boiling tower tower top material and de- high boiling tower materials at bottom of tower；
The benzaldehyde lightness-removing column being connected to at the top of the de- high boiling tower, for the de- high boiling tower tower top material rectifying, obtaining
Benzaldehyde lightness-removing column tower top material and benzaldehyde lightness-removing column materials at bottom of tower；
The benzaldehyde rectifying column being connected to benzaldehyde lightness-removing column bottom, for benzaldehyde lightness-removing column materials at bottom of tower essence
It evaporates, obtains benzaldehyde finished product and benzaldehyde rectifying column materials at bottom of tower；
The oxidation unit includes oxidizing tower, circulating pump and steam generator, and the oxidizing tower is externally provided with chuck, the oxidizing tower
It is interior to be equipped with coil pipe；
The bottom of the oxidizing tower passes sequentially through the side of the circulating pump and steam generator with the oxidizing tower close to top
Connection exchanges heat for most of oxidation solution to be pumped to steam generator through cycle with water, after obtaining steam and heat exchange
Oxidation solution, the oxidation solution after the heat exchange are back in the oxidizing tower；
The bottom of the oxidizing tower is connected to the toluene flash column, is dodged for sending oxidation solution described in small part to the toluene
It steams and is flashed in tower；
Added with soft water in the chuck, coil pipe and steam generator, toluene and air exothermic heat of reaction under the action of catalyst, reaction
Heat is recycled by least one byproduct steam of chuck, coil pipe and steam generator, reaction heat；
The top of the oxidizing tower is equipped with feed inlet and exhaust port, and the feed inlet is for being continuously passed through toluene and catalysis
Agent, the exhaust port is for the tail gas to be discharged；
The top of the toluene flash column is connected to the feed inlet, for the toluene flash column tower top material to be back to institute
It states in oxidizing tower；
The top of the benzaldehyde lightness-removing column is connected to the feed inlet, for returning to the benzaldehyde lightness-removing column tower top material
To in the oxidizing tower；
The bottom of the benzaldehyde rectifying column is connected to the feed inlet, for returning to the benzaldehyde rectifying column materials at bottom of tower
To in the oxidizing tower；
The device of the production benzaldehyde further includes multi-stage condensing device and multi-stage absorption device, the multi-stage condensing device difference
It is connected to the exhaust port, multi-stage absorption device and feed inlet.
2. a kind of method producing benzaldehyde, which is characterized in that include the following steps：
From oxidation tower top continuous feed, air is made from the continuous feed of oxidizing tower bottom, toluene and air in catalyst for toluene, catalyst
With lower successive reaction, tail gas and oxidation solution are formed, the charging proportioning of the air and toluene is 150 Nm3 ~250Nm3:
1000kg, reaction time are 4 ~ 5 hours, and reaction temperature is 145 DEG C ~ 155 DEG C, and reaction pressure is 600 kPa ~ 800kPa,
The catalyst is the aqueous solution of cobalt benzoate, and the mass ratio of cobalt benzoate and water is 1 in the cobalt benzoate aqueous solution:8~
15, a concentration of 40 ppm ~ 100ppm of metal cobalt ions in the reaction system；
After most of oxidation solution is exchanged heat with water, the oxidation solution after obtaining steam and exchanging heat, the oxidation solution after the heat exchange
It returns and participates in the successive reaction；
Oxidation solution described in small part is continuously entered and is flashed in the middle part of toluene flash column, toluene flash column tower top material is obtained
Absolute pressure with toluene flash column materials at bottom of tower, the toluene flash column is 100kPa ~ 120kPa, and toluene flashes column overhead temperature
Degree is 102 DEG C ~ 150 DEG C；
The toluene flash column materials at bottom of tower, which enters, takes off rectifying in the middle part of high boiling tower, obtains de- high boiling tower tower top material and de- high boiling tower
Materials at bottom of tower, the de- high boiling tower absolute pressure of top of the tower are 10kPa ~ 40kPa, and tower top temperature is 130 DEG C ~ 165 DEG C；
The de- high boiling tower tower top material enters rectifying in the middle part of benzaldehyde lightness-removing column, obtains benzaldehyde lightness-removing column tower top material and benzene
Formaldehyde lightness-removing column materials at bottom of tower, the benzaldehyde lightness-removing column absolute pressure of top of the tower be 15kPa ~ 60kPa, tower top temperature be 54 DEG C ~
110℃；
The benzaldehyde lightness-removing column materials at bottom of tower enters rectifying in the middle part of benzaldehyde rectifying column, obtains benzaldehyde finished product and benzaldehyde essence
Tower materials at bottom of tower is evaporated, the benzaldehyde rectifying column tower top absolute pressure is 15kPa ~ 50kPa, and tower top temperature is 113.5 DEG C ~ 150
℃。
3. the method for production benzaldehyde according to claim 2, which is characterized in that the method for the production benzaldehyde is also wrapped
Include following steps：
The toluene flash column tower top material is returned and participates in the successive reaction；
The benzaldehyde lightness-removing column tower top material is returned and participates in the successive reaction；
The benzaldehyde rectifying column materials at bottom of tower is returned and participates in the successive reaction.
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| CN106977379A (en) * | 2017-03-23 | 2017-07-25 | 南京大学盐城环保技术与工程研究院 | High-grade p-t-Butylbenzaldehyde preparation method and preparation facilities |
| CN107032969A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that a kind of liquid-phase oxidation of toluene prepares benzaldehyde |
| CN107032970A (en) * | 2017-05-25 | 2017-08-11 | 钦州学院 | The technique that liquid-phase oxidation of toluene prepares benzaldehyde |
| CN108151345A (en) * | 2017-07-25 | 2018-06-12 | 武汉有机实业有限公司 | Heat recovery method and its device are reacted during toluene liquid phase catalytic oxidation |
| CN111217671A (en) * | 2018-11-23 | 2020-06-02 | 南京延长反应技术研究院有限公司 | Methyl aromatic hydrocarbon oxidation reaction system and use method thereof |
| CN110283068A (en) * | 2019-06-05 | 2019-09-27 | 华南理工大学 | A kind of benzoic acid process units reacting thermal drivers air compressor |
| CN111606790B (en) * | 2020-06-02 | 2023-06-09 | 武汉有机实业有限公司 | System and method for continuously producing high-quality high-selectivity benzaldehyde and benzoic acid by using jet loop reactor |
| CN112047823A (en) * | 2020-07-27 | 2020-12-08 | 南京延长反应技术研究院有限公司 | Preparation system and method of halogenated benzaldehyde |
| CN113582825B (en) * | 2021-07-05 | 2023-10-24 | 武汉有机实业有限公司 | Method for recovering food-grade benzaldehyde from benzoic acid rectification low-boiling-point substances |
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| CN104974034A (en) * | 2014-04-10 | 2015-10-14 | 中国石化扬子石油化工有限公司 | Method of two-column separation of benzoic acid, benzaldehyde and methylbenzene |
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