CN114105742B - System and method for continuously preparing acetophenone - Google Patents
System and method for continuously preparing acetophenone Download PDFInfo
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- CN114105742B CN114105742B CN202111676063.5A CN202111676063A CN114105742B CN 114105742 B CN114105742 B CN 114105742B CN 202111676063 A CN202111676063 A CN 202111676063A CN 114105742 B CN114105742 B CN 114105742B
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 152
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000630 rising effect Effects 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 230000003068 static effect Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 238000000066 reactive distillation Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001174 ascending effect Effects 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000004821 distillation Methods 0.000 abstract description 7
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000010517 secondary reaction Methods 0.000 description 15
- 208000012839 conversion disease Diseases 0.000 description 13
- 239000003921 oil Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供一种连续制备苯乙酮的系统和方法，以乙苯为原料，依次经过至少一级精馏反应；每级精馏反应中，物料经与部分气相充分混合进入反应精馏塔，并与自塔内底部上升的气相接触反应，塔顶采出以水和乙苯为主的混合气相，经冷凝和分相，冷凝液中油相返回塔顶，冷凝液中水相作为废水采出，塔釜采出反应液一部分送入下级精馏反应，另一部分作为循环物料经控温返回反应精馏塔上部，最后一级精馏反应中塔釜采出反应液未作为循环物料的部分作为产品采出。本发明具有反应选择性好，无危废产生，节能环保，连续操作易于大规模生产等特点。
The present invention provides a system and method for continuously preparing acetophenone, using ethylbenzene as a raw material, and sequentially undergoing at least one level of distillation reaction; in each level of distillation reaction, the material is fully mixed with part of the gas phase and enters a reaction distillation tower, and is contacted and reacted with the gas phase rising from the bottom of the tower, and a mixed gas phase mainly composed of water and ethylbenzene is extracted from the top of the tower, and after condensation and phase separation, the oil phase in the condensate returns to the top of the tower, and the water phase in the condensate is extracted as wastewater, and a part of the reaction liquid extracted from the tower bottom is sent to the lower distillation reaction, and the other part is returned to the upper part of the reaction distillation tower as a circulating material through temperature control, and the part of the reaction liquid extracted from the tower bottom in the last level of distillation reaction that is not used as a circulating material is extracted as a product. The present invention has the characteristics of good reaction selectivity, no hazardous waste generation, energy saving and environmental protection, and continuous operation and easy large-scale production.
Description
Technical Field
The invention relates to the field of organic matter synthesis, in particular to a system and a method for continuously preparing acetophenone.
Background
Acetophenone, methyl phenyl ketone and acetophenone are important chemical material. Is the simplest aromatic ketone in which the benzene ring is directly attached to the carbonyl group. It exists in free state in some plant essential oils, is colorless crystal or pale yellow oily liquid, and has pungent smell like fructus crataegi aroma. Is an intermediate widely applied to perfume production, and can be used as an organic solvent to be mixed with other solvents. Can also be used in medicine, and has hypnotic effect.
The general production method of acetophenone comprises (1) Friedel-crafts acylation reaction, namely, benzene reacts with acetyl chloride, acetic anhydride or acetic acid to generate acetophenone by using a large amount of aluminum trichloride as a catalyst. Although the method can obtain acetophenone products with higher purity, a great amount of hazardous waste is generated in the reaction process, and the method is quite environment-friendly. (2) The method for preparing acetophenone by ethylbenzene oxidation uses oxidants such as oxygen, potassium permanganate, ozone, etc. The method is generally adopted at present, but the production is basically carried out by intermittent reaction at the present stage, and the method has the advantages of more side reactions, low reaction selectivity and higher subsequent refining difficulty due to long-time reaction at higher temperature and pressure. (3) Patent No. CN102976912B, entitled "preparation method of acetophenone", provides a method for preparing acetophenone by oxidation with molecular oxygen-containing gas using sec-butylbenzene as raw material. The method is a weight reduction reaction, the economy is lower than that of adopting ethylbenzene as a raw material, alkali liquor is required to be added as a slow release agent, and hazardous waste is generated.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a system and a method for continuously preparing acetophenone, which have the characteristics of good reaction selectivity, no hazardous waste, energy conservation, environmental protection, continuous operation, easy mass production and the like.
The invention firstly provides a system for continuously preparing acetophenone, which comprises at least one stage of rectifying component, wherein each stage of rectifying component comprises a reaction rectifying tower, an ejector and a mixer are sequentially arranged on a feeding pipeline of the reaction rectifying tower, a top discharge port of the reaction rectifying tower is sequentially connected with a condenser and a phase separator, one discharge branch of the phase separator is returned to be connected with the top of the reaction rectifying tower, the other branch is taken as a top extraction branch, a bottom discharge pipeline of the reaction rectifying tower is divided into two branches, one branch returns to the upper part of the reaction rectifying tower and is taken as a circulating pipeline, the other branch is connected with a feeding pipeline of the reaction rectifying tower of the next stage of rectifying component, and the other branch which is not taken as the circulating pipeline is taken as a material extraction pipeline in the two branches of the bottom discharge pipeline of the last stage of rectifying component.
For convenience of description, in the system, each stage of rectifying assembly arranged according to the flow direction sequence of the materials can be sequentially a primary rectifying assembly, a secondary rectifying assembly and a tertiary rectifying assembly, the equipment in each stage of rectifying component is also distinguished according to the grading sequence, such as a first-stage reactive rectifying tower, a second-stage reactive rectifying tower, a third-stage reactive rectifying tower, a first-stage condenser, a second-stage condenser, a third-stage condenser and the like.
The reaction preheater is arranged on the feeding pipeline of the reaction rectifying tower in the first-stage rectifying component and is connected with the ejector and the mixer in sequence and used for preheating materials, and the reaction preheater is not arranged in each subsequent-stage rectifying component.
Wherein, on the feed pipeline of the reactive distillation column in the primary distillation component, a feed pump is arranged in front of the ejector and used for conveying raw materials in the system.
Wherein, the circulating pipeline of each stage of rectifying component is sequentially provided with a reaction tower cooler and a reaction tower heater for maintaining and controlling the temperature of circulating materials. Because the reaction is exothermic, heat is required to be removed when the reaction heat is too high, and heat is required to be supplemented when the reaction heat is too low or the heat is insufficient, the ethylene is sequentially arranged on the circulating pipeline to form a reaction tower cooler and a reaction tower heater, so that the heat fluctuation requirement of circulating materials can be effectively met.
And the circulating pipeline of each stage of rectifying component is also provided with a reaction tower circulating pump for providing circulating or outputting power.
The lower part of the reaction rectifying tower of each stage of rectifying component is also provided with an air/oxygen inlet pipeline and an inert gas inlet pipeline, the air/oxygen inlet pipeline is also provided with a branch communicated with the ejector and used for providing jet power gas for the ejector, the gas and the materials form particles to promote the mixing effect through the jet, and the mixture can be further fully and uniformly mixed through the mixer, so that the improvement of the reaction efficiency and the conversion rate of the materials is facilitated.
Wherein the mixer is a static mixer.
Wherein, the rectification components are preferably more than two groups, most preferably three groups, and can achieve better conversion rate and selectivity of acetophenone preparation through conditioning.
The invention also provides a method for continuously preparing acetophenone by adopting the system, which comprises the following steps that ethylbenzene is used as a raw material, at least one stage of rectification reaction is sequentially carried out, in each stage of rectification reaction, the material is fully mixed with part of gas phase, enters a reaction rectification tower, and is in contact reaction with the gas phase rising from the inner bottom of the tower, the mixed gas phase mainly comprising water and ethylbenzene is extracted from the tower top, the oil phase in condensate returns to the tower top after condensation and phase separation, the water phase in condensate is extracted as wastewater, one part of reaction liquid extracted from the tower bottom is sent to the lower stage of rectification reaction, the other part of reaction liquid is returned to the upper part of the reaction rectification tower as circulating material through temperature control, and the part of reaction liquid extracted from the tower bottom in the last stage of rectification reaction is extracted as a product.
Wherein the material also comprises a catalyst, the catalyst can be one or more of vanadium, cobalt and manganese, and the dosage of the catalyst can be 0.1-10wt% of ethylbenzene.
In each stage of rectification reaction, partial gas phase fully mixed with the materials before entering the reactive rectification tower is oxygen-containing gas, the oxygen-containing gas and the inert gas are mixed in a spray mode and can be further mixed in a static mixer, and the gas phase rising at the bottom of the tower comprises the oxygen-containing gas and the inert gas. The oxygen-containing gas is used as an oxidant to participate in the oxidation reaction and ethylbenzene to generate acetophenone, and the inert gas does not participate in the reaction, so that the oxygen concentration in the gas can be diluted, the side reaction of excessive oxidation is avoided, the gas phase flow rate in the tower can be improved, and the gas-liquid contact effect is ensured. The oxygen-containing gas can be one or more of oxygen, air or ozone, the inert gas can be one or more of nitrogen and helium, and the dosage ratio of the oxygen-containing gas to the inert gas can be 10:1-1:10. In the reactive distillation column, the flow ratio of the circulating material to the ascending gas phase at the bottom in the column is (1.5-4): 1, preferably (1.7-2): 1.
The reaction rectifying tower can be a plate tower or a packed tower, the plate tower internals can be sieve plates, floating valves, bubble caps, vertical sieve plates or other types of trays, the packed tower internals can be structured packing or random packing, and the existing conventional rectifying tower can meet the requirements in the various towers.
The temperature in each stage of reactive rectifying tower is controlled to be 50-150 ℃, the pressure is controlled to be 0.1 MPaG-5.0 MpaG, the residence time is 1-20 h, the concentration of acetophenone in reaction liquid extracted from a tower kettle is 5% -95%, and the feeding temperature of each stage of reactive rectifying tower is also controlled to be 50-150 ℃. The rectification reaction at each stage can reach a reaction conversion rate of more than 30% -95% and a selectivity of more than 85% under the condition control.
The rectification reaction of the invention is preferably two stages or more, preferably three stages, and the temperature in each stage of the reactive rectification tower is controlled at 110-140 ℃ and the pressure is controlled at 0.2 MPaG-0.5 MPaG. The optimized multistage rectification reaction and conditions can further improve the reaction conversion rate, wherein the secondary reaction can reach more than 70% of the reaction conversion rate, and the tertiary reaction can reach more than 85% of the reaction conversion rate.
Wherein, the mixed gas phase mainly comprising water and ethylbenzene extracted from the top of each stage of reactive rectifying tower is condensed and split in phase, and a part of small amount of non-condensed gas phase can be discharged as tail gas.
The method for preparing acetophenone continuously by adopting the reactive distillation method can avoid side reaction to the greatest extent, improve the reaction selectivity and gradually improve the reaction conversion rate by optimizing the reaction process conditions of each stage. The raw materials are simple in components, the impurity types in the final reaction product are few, the content is low, the subsequent refining and purifying difficulty is reduced, the process of washing alkali liquor to remove acid impurities can be effectively avoided, and the effects of energy conservation and emission reduction are achieved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of the overall structure of an example of a three-stage rectification reaction according to the present invention.
Wherein, the device comprises a 1-feeding pump, a 2-first-stage reaction tower ejector, a 3-first-stage reaction tower static mixer, a 4-reaction preheater, a 5-first-stage reaction rectifying tower, a 6-first-stage reaction tower condenser, a 7-first-stage reaction tower split-phase tank, a 8-first-stage reaction tower circulating pump, a 9-first-stage reaction tower cooler, a 10-first-stage reaction tower heater, a 11-second-stage reaction tower ejector, a 12-second-stage reaction tower static mixer, a 13-second-stage reaction rectifying tower, a 14-second-stage reaction tower condenser, a 15-second-stage reaction tower split-phase tank, a 16-second-stage reaction tower circulating pump, a 17-second-stage reaction tower cooler, a 18-second-stage reaction tower heater, a 19-third-stage reaction tower ejector, a 20-third-stage reaction tower static mixer, a 21-third-stage reaction rectifying tower, a 22-third-stage reaction tower condenser, a 23-third-stage reaction tower split-phase tank, a 24-third-stage reaction tower circulating pump, a 25-third-stage reaction tower cooler and a 26-third-stage reaction tower heater.
FIG. 2 shows the effect of different reaction temperatures on the conversion and selectivity of the reaction at a fixed pressure (0.4 MpaG).
FIG. 3 shows the effect of different reaction pressures on the conversion and selectivity of the reaction at a fixed temperature (140 ℃).
Detailed Description
The invention will be further described with reference to the accompanying drawings, without limiting the scope of the invention.
As shown in FIG. 1, an overall schematic diagram of an example of a three-stage rectification reaction is provided, and on the basis of the schematic diagram, the system structure of one-stage, two-stage, and more than one-stage rectification reactions can be deduced. The ethylbenzene raw material and a small amount of catalyst can sequentially enter a first-stage reaction rectifying tower 5 through a feed pump 1, a first-stage reaction tower ejector 2, a first-stage reaction tower static mixer 3 and a reaction preheater 4, oxygen-containing gas and inert gas enter from the bottom of the first-stage reaction rectifying tower 5 and fully contact with materials for reaction, a mixed gas phase extracted from the tower top is condensed through a first-stage reaction tower condenser 6 and enters a first-stage reaction tower split-phase tank 7, an oil phase returns to the tower top for circulation, a water phase is discharged as wastewater, a small amount of noncondensable gas phase is discharged as tail gas, a reaction liquid is extracted from the tower bottom through a first-stage reaction tower circulating pump 8, a part of reaction liquid returns to the tower top for material circulation through a first-stage reaction tower cooler 9 and a temperature control of a first-stage reaction tower heater 10, and a part of reaction liquid enters a second-stage reaction rectifying tower 13 through a second-stage reaction tower ejector 11 and a second-stage reaction tower static mixer 12 in sequence. Oxygen-containing gas and inert gas enter from the bottom of the secondary reaction rectifying tower 13, fully contact with materials to react, the mixed gas phase extracted from the tower top is condensed by a secondary reaction tower condenser 14 to enter a secondary reaction tower split-phase tank 15, the oil phase returns to the tower top to circulate, the water phase is discharged as waste water, a small amount of non-condensable gas phase is discharged as tail gas, the tower bottom extracts reaction liquid by a secondary reaction tower circulating pump 16, a part of reaction liquid is returned to the tower top by the temperature control of a secondary reaction tower cooler 17 and a secondary reaction tower heater 18 to circulate materials, and a part of reaction liquid is sent to the next stage of rectifying reaction and sequentially enters a tertiary reaction rectifying tower 21 through a tertiary reaction tower ejector 19 and a tertiary reaction tower static mixer 20. Oxygen-containing gas and inert gas enter from the bottom of the three-stage reaction rectifying tower 21, fully contact with materials to react, the mixed gas phase extracted from the tower top is condensed by a three-stage reaction tower condenser 22 to enter a three-stage reaction tower split-phase tank 23, the oil phase returns to the tower top to circulate, the water phase is discharged as waste water, a small amount of non-condensable gas phase is discharged as tail gas, the tower bottom extracts reaction liquid by a three-stage reaction tower circulating pump 24, a part of reaction liquid returns to the tower top to circulate materials by controlling the temperature of a three-stage reaction tower cooler 25 and a three-stage reaction tower heater 26, and a part of reaction liquid is extracted as a product.
The system and method of the present disclosure are described in further detail below in connection with specific embodiments.
Example 1
The acetophenone is continuously produced by the method and the system, and the single-stage reaction rectification system is adopted in the embodiment, and a specific flow is as follows:
Ethylbenzene is added with 1wt% of vanadyl acetylacetonate catalyst, pressurized by a raw material pump and enters an ejector, the flow is controlled to be 0.5m 3// h, then enters a reaction preheater through a static mixer, the outlet temperature of the preheater is 135 ℃, and finally enters the middle part of a reaction rectifying tower. The diameter of the reaction rectifying tower is 800mm, the height of the tower is 25200mm, the tower internals are three-dimensional jet trays, the tray spacing is 450mm, and the number of the trays is 40 layers. The material control circulation flow of the tower bottom is 60m 3/h, the temperature of the circulation liquid is strictly controlled to be 140 ℃ through a cooler and a heater, and the pressure of the reactive rectifying tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 20Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 8Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower kettle is controlled at 53.5%, and part of the acetophenone content is used as a reaction product and sent to the subsequent refining process. The final reaction conversion was 57.90% with a selectivity of 85.9%.
To investigate the effect of different reaction conditions on reaction conversion and selectivity, experimental comparisons were made for different reaction conditions in a single stage reactive distillation system, and the results are shown in Table 1. FIGS. 2-3 also show that different pressures and temperatures have an effect on reaction conversion and selectivity, while with some reduction in selectivity, reaction conversion will increase, and therefore it is desirable to optimize the multistage reaction conditions so that both reaction conversion and selectivity can reach equilibrium at higher levels. The reaction temperature at the bottom of the reaction has higher selectivity and lower conversion rate at one stage, but as the reaction stage number increases, the conversion rate is accumulated, the reaction temperature can be properly reduced, and multi-stage rectification can be adopted to accumulate better total conversion rate.
TABLE 1 influence of different reaction conditions on reaction conversion and selectivity
Example two
The acetophenone is continuously produced by the method and the system, and the two-stage serial reaction rectification system is adopted in the embodiment, and the specific flow is as follows:
Ethylbenzene is added with 1wt% of vanadyl acetylacetonate catalyst, pressurized by a raw material pump and enters an ejector, the flow rate is controlled to be 1m 3// h, then enters a reaction preheater through a static mixer, the outlet temperature of the preheater is 135 ℃, and finally enters the middle part of a first-stage reaction tower. The diameter of the primary reaction tower is 1000mm, the height of the tower is 23500mm, tower internals are three-dimensional jet trays, the tray spacing is 500mm, and the number of the trays is 30 layers. The circulating flow rate of the tower kettle is 80m 3/h, the temperature of the circulating liquid is strictly controlled to be 120 ℃ through a cooler and a heater, and the pressure of the first-stage reaction tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 30Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 15Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower bottom is controlled at 40 percent, and the reaction liquid is sent to a secondary reaction tower.
The material from the primary reaction tower enters the ejector and then passes through the static mixer to enter the secondary reaction tower. The diameter of the secondary reaction tower is 1000mm, the height of the tower is 18500mm, tower internals are three-dimensional jet trays, the tray spacing is 500mm, and the number of the trays is 20 layers. The circulating flow rate of the tower kettle is 80m 3/h, the temperature of the circulating liquid is strictly controlled to be 125 ℃ through a cooler and a heater, and the pressure of the primary reaction tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 30Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 15Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower bottom is controlled at 68.9 percent, and the reaction liquid is sent to a three-stage reaction tower. The final reaction conversion was 77.2% with a selectivity of 86.3%.
Example III
The acetophenone is continuously produced by the method and the system, and the embodiment adopts a three-stage series reaction rectifying system, and the specific flow is as follows:
Ethylbenzene is added with 1wt% of vanadyl acetylacetonate catalyst, pressurized by a raw material pump and enters an ejector, the flow rate is controlled to be 1m 3// h, then enters a reaction preheater through a static mixer, the outlet temperature of the preheater is 135 ℃, and finally enters the middle part of a first-stage reaction tower. The diameter of the primary reaction tower is 1000mm, the height of the tower is 23500mm, tower internals are three-dimensional jet trays, the tray spacing is 500mm, and the number of the trays is 30 layers. The circulating flow rate of the tower bottom is controlled to be 80m3/h, the temperature of circulating liquid is strictly controlled to be 140 ℃ through a cooler and a heater, and the control pressure of the first-stage reaction tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 30Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 15Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower bottom is controlled at 40 percent, and the reaction liquid is sent to a secondary reaction tower.
The material from the primary reaction tower enters the ejector and then passes through the static mixer to enter the secondary reaction tower. The diameter of the secondary reaction tower is 1000mm, the height of the tower is 18500mm, tower internals are three-dimensional jet trays, the tray spacing is 500mm, and the number of the trays is 20 layers. The circulating flow rate of the tower kettle is 80m 3/h, the temperature of the circulating liquid is strictly controlled to be 125 ℃ through a cooler and a heater, and the pressure of the primary reaction tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 30Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 15Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower bottom is controlled at 68 percent, and the reaction liquid is sent to a three-stage reaction tower.
The material from the secondary reaction tower enters the ejector and then enters the tertiary reaction tower through the static mixer. The diameter of the secondary reaction tower is 800mm, the height of the tower is 18500mm, tower internals are three-dimensional jet trays, the tray spacing is 500mm, and the number of the trays is 20 layers. The circulating flow rate of the tower kettle is controlled to be 60m 3/h, the temperature of the circulating liquid is strictly controlled to be 125 ℃ through a cooler and a heater, and the pressure of the primary reaction tower is controlled to be 0.4MPaG. The air flow rate of the tower kettle is controlled to be 20Nm 3// h, and the nitrogen flow rate of the tower kettle is controlled to be 10Nm 3// h. The gas phase of the mixture of water extracted from the top of the tower and ethylbenzene enters a condenser, condensate enters a phase separator, the oil phase returns to the top of the tower, and the water phase is extracted as wastewater. Nitrogen and other non-condensable gases are sent to a tail gas treatment system. The acetophenone content in the reaction liquid extracted from the tower kettle is controlled to be 80.6 percent, and the acetophenone is taken as a reaction product to be sent to the subsequent refining process. The final reaction conversion was 89.7% with a selectivity of 85.7%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. In each stage of rectification reaction, the material is fully mixed with partial gas phase, enters a reaction rectification tower, and is contacted with the gas phase rising from the inner bottom of the tower for reaction, the mixed gas phase mainly comprising water and ethylbenzene is extracted from the tower top, the oil phase in condensate returns to the tower top after condensation and phase separation, the water phase in condensate is extracted as waste water, one part of the reaction liquid extracted from the tower bottom is sent to the next stage of rectification reaction, the other part of the reaction liquid is returned to the upper part of the reaction rectification tower as circulating material through temperature control, and the part of the reaction liquid extracted from the tower bottom in the last stage of rectification reaction is extracted as a product;
the material also comprises a catalyst, wherein the catalyst is one or more of vanadium, cobalt and manganese, and the dosage of the catalyst is 0.1-10wt% of ethylbenzene;
in each stage of rectification reaction, partial gas phase fully mixed with the materials before entering the reactive rectification tower is oxygen-containing gas;
the rectification reaction is carried out at two or more stages, the temperature in each stage of the reactive rectification tower is controlled at 110-140 ℃, and the pressure is controlled at 0.2 MPaG-0.5 MpaG.
2. The process for continuously preparing acetophenone according to claim 1, wherein in each stage of the rectification reaction, the oxygen-containing gas is thoroughly mixed with the material in the form of a jet before entering the reactive rectification column and is further mixed in a static mixer;
The gas phase rising at the bottom in the tower comprises oxygen-containing gas and inert gas, wherein the oxygen-containing gas is one or more of oxygen, air or ozone, the inert gas is one or more of nitrogen and helium, and the dosage ratio of the oxygen-containing gas to the inert gas is 10:1-1:10.
3. The process for continuously preparing acetophenone according to claim 1, wherein the flow ratio of the circulating material to the ascending gas phase at the bottom in the reaction rectifying column is (1.5-4): 1.
4. The process for continuously producing acetophenone according to claim 1, wherein the flow ratio of the circulating material to the ascending gas phase at the bottom in the reaction rectifying column is (1.7-2): 1.
5. The method for continuously preparing acetophenone according to claim 1, wherein the reactive distillation column is a plate column or a packed column, the plate column internals are sieve plates, float valves, bubble caps, or vertical sieve plates, and the packed column internals are structured packing or random packing.
6. The method for continuously preparing acetophenone according to claim 1, wherein the retention time in each stage of reactive distillation column is 1-20 h, the concentration of acetophenone in the reaction liquid extracted from the column bottom is 5% -95%, and the feeding temperature of each stage of reactive distillation column is also controlled to be 50-150 ℃.
7. The process for continuously preparing acetophenone according to claim 1, wherein the rectification reaction is three stages.
8. The process for continuously producing acetophenone according to claim 1, wherein a small amount of the non-condensed gas phase is discharged as a tail gas after condensing and phase-separating a mixed gas phase mainly composed of water and ethylbenzene withdrawn from the top of each stage of the reactive distillation column.
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| CN110833844B (en) * | 2019-10-28 | 2023-07-07 | 扬州大学 | Application of cobalt carbonate in preparing acetophenone by ethylbenzene catalytic oxidation under solvent-free catalysis of molecular oxygen |
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