CN115282913B - Reaction system and method for preparing methyl propionate - Google Patents
Reaction system and method for preparing methyl propionate Download PDFInfo
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- CN115282913B CN115282913B CN202210970158.6A CN202210970158A CN115282913B CN 115282913 B CN115282913 B CN 115282913B CN 202210970158 A CN202210970158 A CN 202210970158A CN 115282913 B CN115282913 B CN 115282913B
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 103
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229940017219 methyl propionate Drugs 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 183
- 238000005886 esterification reaction Methods 0.000 claims abstract description 62
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000005977 Ethylene Substances 0.000 claims abstract description 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims description 49
- SICCRERQCOIGDC-UHFFFAOYSA-N methanol;methyl propanoate Chemical compound OC.CCC(=O)OC SICCRERQCOIGDC-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 45
- 239000012071 phase Substances 0.000 claims description 28
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 9
- 239000011552 falling film Substances 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- -1 nitrolacquers Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/148—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step in combination with at least one evaporator
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of industrial production of methyl propionate, in particular to a reaction system and a method for preparing methyl propionate. The system comprises a carbonyl esterification reaction device, an evaporator and a first rectifying tower which are sequentially communicated; the evaporator comprises a first output port and a second output port, the first output port is communicated with a feed inlet of the carbonyl esterification reaction device, and the second output port is communicated with a feed inlet of the first rectifying tower; the carbonyl esterification reaction device comprises a first stirring reaction kettle, a super-gravity rotating bed reactor and a second stirring reaction kettle which are sequentially communicated. When the reaction system works, ethylene, CO and first methanol sequentially enter the first stirring reaction kettle, the super-gravity rotating bed reactor and the second stirring reaction kettle to carry out carbonyl esterification reaction, so that the conversion rate of methyl propionate can be greatly improved, the full utilization of resources is facilitated, and large-scale industrial production can be realized.
Description
Technical Field
The invention relates to the technical field of industrial production of methyl propionate, in particular to a reaction system and a method for preparing methyl propionate.
Background
Methyl propionate is an organic compound, has a chemical formula of C4H8O2, is colorless transparent liquid, is slightly soluble in water, and is miscible with ethanol and diethyl ether. Are commonly used as solvents for nitrocellulose, nitrolacquers, paints, varnishes and the like, but also for fragrances and flavours, and as intermediates in organic syntheses, such as the further condensation with formaldehyde to produce methyl methacrylate. At present, research on producing methyl propionate by using ethylene as a raw material through carbonyl esterification reaction has made a breakthrough, but the existing reaction conditions for synthesizing methyl propionate by using ethylene homogeneous phase hydro-ester group are harsh, the conversion rate is low, the purity of the obtained methyl propionate is low, the selectivity is poor, and large-scale industrial application cannot be realized. Therefore, how to improve the conversion rate of methyl propionate prepared by using ethylene as a raw material and realize large-scale industrial application is a technical problem to be solved urgently by current researchers.
Disclosure of Invention
The first aim of the invention is to provide a reaction system for preparing methyl propionate, which solves the technical problems that the conversion rate of preparing methyl propionate by taking ethylene as a raw material is low and large-scale industrialized application cannot be realized in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a reaction system for preparing methyl propionate comprises a carbonyl esterification reaction device, an evaporator and a first rectifying tower which are sequentially communicated;
the evaporator comprises a first output port and a second output port, the first output port is communicated with the feed inlet of the carbonyl esterification reaction device, and the second output port is communicated with the feed inlet of the first rectifying tower;
the carbonyl esterification reaction device comprises a first stirring reaction kettle, a hypergravity rotating bed reactor and a second stirring reaction kettle which are sequentially communicated, wherein a discharge hole of the second stirring reaction kettle is communicated with a feed inlet of the evaporator.
Further, the reaction system further comprises a raw material purifying device, and a discharge port of the raw material purifying device is communicated with a feed port of the carbonyl esterification reaction device.
Further, the reaction system further comprises a pressure-variable rectifying device, the pressure-variable rectifying device comprises a second rectifying tower, a discharge port at the top of the first rectifying tower is communicated with a feed inlet of the second rectifying tower, and a discharge port at the bottom of the second rectifying tower is communicated with a feed inlet of the carbonyl esterification reaction device.
Further, the pressure swing rectifying device also comprises a third rectifying tower; the discharge port of the top of the second rectifying tower is communicated with the feed port of the third rectifying tower, and the discharge port of the top of the third rectifying tower is communicated with the feed port of the second rectifying tower.
The second purpose of the invention is to provide a method for preparing methyl propionate, which aims to solve the technical problems that the conversion rate of preparing methyl propionate by taking ethylene as a raw material is low and large-scale industrial application cannot be realized in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for the preparation of methyl propionate comprising the steps of:
s1: ethylene, CO and first methanol are sent into a carbonyl esterification reaction device for carbonyl esterification reaction, and the ethylene, CO and first methanol sequentially enter a first stirring reaction kettle, a super-gravity rotating bed reactor and a second stirring reaction kettle for reaction, so that a reaction mixture is obtained;
s2: introducing the reaction mixture obtained in the step 1 into an evaporator for separation, and separating the reaction mixture by the evaporator to obtain a liquid-phase product and a gas-phase product;
s3: the liquid phase product at the bottom of the evaporator is pressurized to return to the carbonyl esterification reaction device for cyclic reaction after the catalyst is supplemented; condensing a gas-phase product at the top of the evaporator, and then introducing the condensed gas-phase product into a rectification system for separation to obtain methyl propionate and second methanol;
s4: and (3) pressurizing the second methanol obtained in the step (3) back into the carbonyl esterification reaction device for cyclic reaction.
Further, the evaporator is configured as a falling film evaporator; the operation pressure of the falling film evaporator is 0.1MPa-0.3MPa, and the operation temperature is 65-105 ℃.
Further, feeding raw material ethylene, raw material CO and raw material methanol into a raw material purifying device for purification, removing sulfur and chlorine impurities in the raw material ethylene and the raw material CO, and deoxidizing the raw material methanol; and conveying the ethylene, the CO and the first methanol generated after the purification to the carbonyl esterification reaction device for reaction.
Further, the rectification system comprises a first rectification tower, and the gas-phase product is introduced into the first rectification tower after being condensed; the operation pressure of the top of the first rectifying tower is 1-1.5 bar, the reflux ratio is 2-4, the gas phase product is separated by the first rectifying tower to obtain a first methyl propionate and a first methyl propionate-methanol mixture, and the first methyl propionate is discharged from a discharge hole at the bottom of the first rectifying tower.
Further, the rectification system also comprises a pressure-variable rectification device, the pressure-variable rectification device comprises a second rectification tower, the first methyl propionate-methanol mixture is discharged from a discharge port at the top of the first rectification tower, and enters the second rectification tower after being condensed; the operating pressure at the top of the second rectifying tower is 1bar, the reflux ratio is 2-4, the second rectifying tower separates the first methyl propionate-methanol mixture to obtain second methanol and a second methyl propionate-methanol mixture, and the second methanol is discharged from a discharge hole at the bottom of the second rectifying tower and enters the carbonyl esterification reaction device.
Further, the pressure swing rectifying device also comprises a third rectifying tower, the second methyl propionate-methanol mixture is discharged from a discharge port at the top of the second rectifying tower, and enters the third rectifying tower after being condensed; the operating pressure at the top of the third rectifying tower is 6bar, the reflux ratio is 2-4, the third rectifying tower separates the second methyl propionate-methanol mixture to obtain a second methyl propionate and a third methyl propionate-methanol mixture, and the second methyl propionate is discharged from a discharge port at the bottom of the third rectifying tower; and discharging the third methyl propionate-methanol mixture from a discharge port at the top of the third rectifying tower and entering the second rectifying tower.
The invention has the beneficial effects that:
the invention provides a reaction system and a method for preparing methyl propionate, wherein the system comprises a carbonyl esterification reaction device, an evaporator and a first rectifying tower which are communicated in sequence; the evaporator comprises a first output port and a second output port, the first output port is communicated with a feed inlet of the carbonyl esterification reaction device, and the second output port is communicated with a feed inlet of the first rectifying tower; the carbonyl esterification reaction device comprises a first stirring reaction kettle, a super-gravity rotating bed reactor and a second stirring reaction kettle which are sequentially communicated. When the reaction system works, ethylene, CO and first methanol enter a carbonyl esterification reaction device and sequentially enter a first stirring reaction kettle, a super-gravity rotating bed reactor and a second stirring reaction kettle to carry out carbonyl esterification reaction, and reaction heat is released while methyl propionate is generated to obtain a reaction mixture; the reaction mixture is discharged from the carbonyl esterification reaction device and enters an evaporator; separating the reaction mixture by an evaporator to obtain a liquid-phase product and a gas-phase product, discharging the liquid-phase product from a first output port, entering a carbonyl esterification reaction device for recycling, discharging the gas-phase product from a second output port, condensing by a condenser, and entering a first rectifying tower; and separating the condensed gas-phase product by the first rectifying tower to obtain first methyl propionate and a first methyl propionate-methanol mixture.
According to the embodiment, the first stirring reaction kettle, the hypergravity rotating bed reactor and the second stirring reaction kettle are arranged in series, so that ethylene, CO and first methanol entering the carbonyl esterification reaction device can fully carry out carbonyl esterification reaction, and the conversion rate of methyl propionate is greatly improved; only 1 hypergravity rotating bed reactor is used in the 3 reactors and is arranged between the first stirring reaction kettle and the second stirring reaction kettle, so that on one hand, the conversion rate is improved, and meanwhile, the operation cost is saved, and on the other hand, the phenomenon that the reaction heat release is too severe due to the fact that the hypergravity rotating bed reactor is placed at the first place of series connection can be avoided; the second stirred tank reactor mainly plays a role in stabilizing gas-liquid two phases except for reaction, so that the reaction mixture discharged from the super-gravity rotating bed reactor can stably enter the evaporator. In addition, the liquid phase product obtained by the separation of the evaporator enters the carbonyl esterification reaction device for recycling, so that the conversion rate of methyl propionate is improved while the cost is saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a reaction system for producing methyl propionate according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a reaction system for preparing methyl propionate according to an embodiment of the present invention, which includes a plurality of rectifying towers.
Icon:
a 1-carbonyl esterification reaction device; 11-a first stirring reaction kettle; 12-a supergravity rotating bed reactor; 13-a second reaction kettle with stirring;
2-an evaporator;
3-a first rectifying tower;
41-ethylene; 42-CO; 431-first methanol; 432-second methanol; 44-the reaction mixture; 45-liquid phase product; 46-gas phase product; 471-first methyl propionate; 472-second methyl propionate; 481-a first methyl propionate-methanol mixture; 482-a second methyl propionate-methanol mixture; 483-a third methyl propionate-methanol mixture;
5-a raw material purifying device;
6-a pressure swing rectifying device; 61-a second rectifying column; 62-a third rectifying tower;
7-a condenser;
8-pump.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, in the description of the present invention, the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
It should be noted that, in the description of the present invention, the terms "connected" and "mounted" should be understood in a broad sense, and for example, may be a fixed connection, a detachable connection, or an integral connection; can be directly connected or connected through an intermediate medium; either mechanically or electrically. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Example 1
The present embodiment provides a reaction system for producing methyl propionate, referring to fig. 1, which comprises a carbonyl esterification reaction apparatus 1, an evaporator 2, and a first rectifying column 3, which are sequentially connected; the evaporator 2 comprises a first output port and a second output port, wherein the first output port is communicated with the feed inlet of the carbonyl esterification reaction device 1, and the second output port is communicated with the feed inlet of the first rectifying tower 3; the carbonyl esterification reaction device 1 comprises a first stirring reaction kettle 11, a hypergravity rotating bed reactor 12 and a second stirring reaction kettle 13 which are sequentially communicated, wherein a discharge hole of the second stirring reaction kettle 13 is communicated with a feed inlet of the evaporator 2.
When the reaction system works, ethylene 41, CO42 and first methanol 431 enter a carbonyl esterification reaction device 1 and sequentially enter a first stirring reaction kettle 11, a hypergravity rotating bed reactor 12 and a second stirring reaction kettle 13, and the carbonyl esterification reaction is carried out under the catalysis of a catalyst, so that reaction heat is released while methyl propionate is generated, and a reaction mixture 44 is obtained; the reaction mixture 44 is discharged from the carbonyl esterification reaction apparatus 1 and enters the evaporator 2; the evaporator 2 separates the reaction mixture 44 to obtain a liquid-phase product 45 and a gas-phase product 46, the liquid-phase product 45 is discharged from a first output port under the action of a pump 8 and enters the carbonyl esterification reaction device 1 for recycling, and the gas-phase product 46 is discharged from a second output port, enters the first rectifying tower 3 after being condensed by a condenser 7; the condensed gas-phase product 46 is separated by the first rectifying tower 3, the first methyl propionate 471 is obtained at the bottom of the tower, and the first methyl propionate-methanol mixture 481 in an azeotropic state is obtained at the top of the tower.
In the embodiment, the first stirring reaction kettle 11, the hypergravity rotating bed reactor 12 and the second stirring reaction kettle 13 are arranged in series, so that the ethylene 41, the CO42 and the first methanol 431 entering the carbonyl esterification reaction device 1 can fully carry out carbonyl esterification reaction, and the conversion rate of methyl propionate is greatly improved; only 1 hypergravity rotating bed reactor 12 is used in the 3 reactors and is arranged between the first stirring reaction kettle 11 and the second stirring reaction kettle 13, so that on one hand, the conversion rate is improved, and meanwhile, the operation cost is saved, and on the other hand, the phenomenon that the reaction heat release caused by the placement of the hypergravity rotating bed reactor 12 at the first place of series connection is too severe can be avoided; the second stirred tank reactor 13 mainly plays a role in stabilizing the gas-liquid two phases except for the reaction, so that the reaction mixture discharged from the super-gravity rotating bed reactor 12 can stably enter the evaporator 2. In addition, the liquid-phase product 45 obtained by separation of the evaporator 2 enters the carbonyl esterification reaction device 1 for recycling, so that the conversion rate of methyl propionate is improved while the cost is saved.
Alternatively, since the main reactions are concentrated in the first stirred tank reactor 11 and the hypergravity rotating bed reactor 12, the first stirred tank reactor 11 and the hypergravity rotating bed reactor 12 are provided with an inner coil heat extraction and an outer circulation heat extraction; namely, the first stirred reactor 11 is a kettle type reactor with stirring and external circulation heat exchange and internal heat exchange coils of the reactor, the super-gravity rotating bed reactor 12 is a super-gravity rotating bed reactor with external circulation heat exchange and internal heat exchange coils, and the second stirred reactor 13 is a kettle type reactor with internal heat exchange coils.
In the initial state, the raw material ethylene, the raw material CO and the raw material methanol contain trace sulfur and chlorine compounds, and a small amount of oxygen is dissolved in the raw material methanol. In order to avoid the influence of impurities in the raw materials on the reaction effect, the conversion rate of the reaction is further improved, the reaction system further comprises a raw material purifying device 5, and a discharge hole of the raw material purifying device 5 is communicated with a feed hole of the carbonyl esterification reaction device 1. Ethylene 41, CO42 and first methanol 431 produced by purifying raw material ethylene, raw material CO and raw material methanol in the raw material purifying apparatus are fed into the carbonyl esterification reaction apparatus 1 and reacted.
Referring to fig. 2, the reaction system further includes a pressure swing rectifying device 6, the pressure swing rectifying device 6 includes a second rectifying tower 61, a discharge port at the top of the first rectifying tower 3 is communicated with a feed port of the second rectifying tower 61, and a discharge port at the bottom of the second rectifying tower 61 is communicated with a feed port of the carbonyl esterification reaction device 1.
When the reaction system works, the first methyl propionate-methanol mixture 481 is discharged from a discharge port at the top of the first rectifying tower 3, and enters the pressure-variable rectifying device 6 after being condensed under the driving of the pump 8; the first methyl propionate-methanol mixture 481 enters a second rectifying tower 61 firstly, the second rectifying tower 61 separates the first methyl propionate-methanol mixture 481, second methanol 432 with purity more than 99% is obtained at the bottom of the tower, and the second methanol 432 is discharged from a discharge port at the bottom of the second rectifying tower 61 and enters a carbonyl esterification reaction device 1 for recycling; the top of the column yields a second methyl propionate-methanol mixture 482 that is azeotropic. In this embodiment, the second rectifying tower 61 further separates the reaction mixture, and the separated methanol enters the carbonyl esterification reaction apparatus 1 for recycling, so that the conversion rate of methyl propionate is improved while saving the cost.
Further, the pressure swing rectifying device 6 further includes a third rectifying tower 62; the discharge port of the top of the second rectifying tower 61 is communicated with the feed port of the third rectifying tower 62, and the discharge port of the top of the third rectifying tower 62 is communicated with the feed port of the second rectifying tower 61.
When the reaction system works, the second methyl propionate-methanol mixture 482 is discharged from a discharge port at the top of the second rectifying tower 61, condensed and enters the third rectifying tower 62; the third rectifying tower 62 separates the second methyl propionate-methanol mixture 482 entering the third rectifying tower, the second methyl propionate 472 with the purity more than 99% is obtained at the bottom of the tower, and the second methyl propionate 472 is discharged from a discharge hole at the bottom of the third rectifying tower 62; the third methyl propionate-methanol mixture 483 with an azeotropic state is obtained at the top of the tower, the third methyl propionate-methanol mixture 483 is discharged from a discharge hole at the top of the third rectifying tower 62, and enters the second rectifying tower 61 for circulating separation after condensation.
In this embodiment, the first rectifying tower 3 is an atmospheric rectifying tower, and the second rectifying tower 61 and the third rectifying tower 62 form a pressure swing rectifying device 6; when the pressure-variable rectifying device is used, most of methyl propionate is firstly separated from the first rectifying tower 3, so that the operation pressure of the subsequent separation of the pressure-variable rectifying device 6 is reduced to the greatest extent; the pressure swing rectifying device 6 performs repeated and cyclic purification and separation on the methyl propionate-methanol mixture discharged from the first rectifying tower 3, and the generated methanol can be recycled, so that the conversion rate of methyl propionate is improved, and the conversion rate of methyl propionate can reach more than 99.9%.
Example two
Referring to fig. 1, the present embodiment provides a method for preparing methyl propionate, comprising the steps of:
s1: ethylene 41, CO42 and first methanol 431 are sent into a carbonyl esterification reaction device 1 for carbonyl esterification reaction, and the ethylene 41, the CO42 and the first methanol 431 sequentially enter a first stirring reaction kettle 11, a super-gravity rotating bed reactor 12 and a second stirring reaction kettle 13 for reaction, so that a reaction mixture 44 is obtained;
s2: introducing the reaction mixture 44 obtained in the step 1 into an evaporator 2 for separation, and separating the reaction mixture 44 by the evaporator 2 to obtain a liquid-phase product 45 and a gas-phase product 46;
s3: the liquid phase product 45 at the bottom of the evaporator 2 is pressurized back to the carbonyl esterification reaction device 1 for cyclic reaction after the catalyst is replenished; the gas-phase product 46 at the top of the evaporator 2 is condensed and then is introduced into a rectification system for separation, so that methyl propionate and second methanol 432 are obtained;
s4: the second methanol 432 obtained in the step 3 is pressurized and returned to the carbonyl esterification reaction apparatus 1 to carry out a cyclic reaction.
Further, raw material ethylene, raw material CO and raw material methanol are sent into a raw material purifying device 5 for purification, sulfur and chlorine impurities in the raw material ethylene and raw material CO are removed, and the raw material methanol is deoxidized; the ethylene 41, CO42 and the first methanol 431 produced after the purification are transferred to the carbonyl esterification reaction apparatus 1 and reacted.
Further, the evaporator 2 is provided as a falling film evaporator; the operation pressure of the falling film evaporator is 0.1MPa-0.3MPa, and the operation temperature is 65-105 ℃. Preferably, the falling film evaporator operates at a pressure of 0.25MPa to 0.3MPa and a corresponding operating temperature of 96 ℃ to 104 ℃.
Further, the mass flow rate of liquid phase extraction at the bottom of the gas collection tank of the evaporator 2 is controlled to be 20-60% of the mass flow rate of gas phase extraction at the top. Preferably, the mass flow rate of the liquid phase withdrawn from the bottom of the gas collection tank of the evaporator 2 is controlled to be 30-50% of the mass flow rate of the gas phase withdrawn from the top.
Referring to fig. 2, the rectification system includes a first rectification column 3, and the vapor phase product 46 is condensed and then introduced into the first rectification column 3; the operation pressure at the top of the first rectifying tower 3 is 1-1.5 bar, the reflux ratio is 2-4, and the first rectifying tower 3 separates the gas phase product 46 to obtain a first methyl propionate 471 and a first methyl propionate-methanol mixture 481.
Preferably, the operating pressure of the first rectification column 3 is from 1 to 1.3bar and the reflux ratio is from 2 to 3.
Further, the rectification system also comprises a pressure-variable rectification device 6; the pressure swing rectifying device 6 comprises a second rectifying tower 61, the first methyl propionate-methanol mixture 481 is discharged from a discharge port at the top of the first rectifying tower 3, and enters the second rectifying tower 61 after being condensed; the operation pressure at the top of the second rectifying tower 61 is 1bar, the reflux ratio is 2-4, the second rectifying tower 61 separates the first methyl propionate-methanol mixture 481 to obtain second methanol 432 and a second methyl propionate-methanol mixture 482, and the second methanol 432 is discharged from a discharge hole at the bottom of the second rectifying tower 61 and enters the carbonyl esterification reaction device 1.
Further, the pressure swing rectifying device 6 further comprises a third rectifying tower 62, the second methyl propionate-methanol mixture 482 is discharged from a discharge hole at the top of the second rectifying tower 61, and enters the third rectifying tower 62 after being condensed; the operation pressure at the top of the third rectifying tower 62 is 6bar, the reflux ratio is 2-4, the third rectifying tower 62 separates the second methyl propionate-methanol mixture 482 to obtain a second methyl propionate 472 and a third methyl propionate-methanol mixture 483, and the second methyl propionate 472 is discharged from a discharge port at the bottom of the third rectifying tower 62; third methyl propionate-methanol mixture 483 is discharged from the discharge port at the top of third rectifying column 62 and enters second rectifying column 61.
In the embodiment, the mol ratio of raw materials of ethylene, CO and methanol is 1-1.5:1:1 (methanol: ethylene: CO); by defining the molar ratio of methanol, ethylene and CO to take part in the reaction, the reaction product methyl propionate and methanol mixture molar ratio is in the interval 2:1 to 5:1. Designing 3 rectification towers in series according to the molar ratio of methyl propionate to methanol in the reaction product; wherein the first rectifying tower 3 is set as an atmospheric rectifying tower, and the second rectifying tower 61 and the third rectifying tower 62 form a pressure swing rectifying device 6; most of methyl propionate is separated from the first rectifying tower 3, the subsequent separation operation pressure is reduced to the greatest extent, methyl propionate-methanol azeotrope generated at the top of the first rectifying tower 3 enters a pressure-variable rectifying device formed by subsequent double towers, the separation of methyl propionate-methanol azeotrope is realized by adopting rectifying towers with different operation pressures, and methanol and methyl propionate with purity more than 99% are respectively obtained at the bottoms of the two towers.
Preferably, the molar ratio of ethylene, CO and methanol as the raw materials is 1.2-1.5:1:1 (methanol: ethylene: CO).
The method is illustrated by the following specific examples:
the raw materials are supplied to the reaction system according to the flow rates of 50kmol/h of ethylene, 50kmol/h of CO and 75kmol/h of methanol, the three raw materials firstly enter a raw material purifying device 5, the raw materials of ethylene and CO are removed of sulfur and chlorine compounds contained in the raw materials, and the raw materials of methanol are removed of a small amount of dissolved oxygen.
Introducing ethylene 41, CO42 and first methanol 431 generated after purification and a recycled liquid phase product 45 containing a catalyst into a carbonyl esterification reaction device 1 formed by connecting a first stirring reaction kettle 11, a hypergravity rotating bed reactor 12 and a second stirring reaction kettle 13 in series for reaction to obtain a reaction mixture 44 of 1.061kmol/h, wherein the methanol accounts for 26.54% and the methyl propionate accounts for 73.46% (mole fraction, the same applies below); the reaction mixture 44 enters a falling film evaporator system, and is separated under the conditions of 0.25MPa and 98.8 ℃ to obtain a liquid phase product 45 of 0.3141kmol/h and a gas phase product 46 of 0.7469 kmol/h; in the gas phase product 46, 33.43% methanol and 66.57% methyl propionate; in the liquid phase product 45, methanol accounts for 10.15 percent, and methyl propionate accounts for 89.85 percent; the liquid phase product 45 is cooled and pressurized, and a small amount of catalyst is supplemented, and then the liquid phase product is recycled to the carbonyl esterification reaction device 1 for recycling, and the gas phase product 46 is cooled and enters a rectification system.
The gas phase product 46 enters the first rectifying tower 3 after being cooled; the operating pressure at the top of the first rectifying tower 3 is 1bar, and the operating reflux ratio is 2.4; after separation, obtaining 0.3669kmol/h of first methyl propionate 471 at the bottom of the tower, wherein the purity is more than or equal to 99.9%; a first methyl propionate-methanol mixture 481 was taken overhead at 0.38kmol/h in an azeotropic state, with methyl propionate representing 65.61% and methanol representing 34.39%.
First methyl propionate-methanol mixture 481 is condensed and introduced into second rectifying column 61; the operating pressure at the top of the second rectifying column 61 is 1bar, and the reflux ratio is 2; after separation, obtaining 0.2483kmol/h second methanol 432 at the bottom of the tower, wherein the purity is more than or equal to 99.3%, and introducing the second methanol 432 into a carbonyl esterification reaction device 1 for recycling; a second methyl propionate-methanol mixture 482 in azeotropic state was taken out from the top of the column at 1.0371kmol/h, wherein methyl propionate was 70.98% and methanol was 29.02%.
The second methyl propionate-methanol mixture 482 is pressurized and then continuously introduced into the third rectification column 62; the operating pressure at the top of the third rectification column 62 was 6bar, the reflux ratio was 2; after separation, methyl propionate is obtained at the bottom of the tower, wherein the purity is more than or equal to 99.3 percent; a third methyl propionate-methanol mixture 483 with 0.9081kmol/h in an azeotropic state is obtained at the top of the tower, wherein methyl propionate accounts for 80.97 percent and methanol accounts for 19.03 percent; the third methyl propionate-methanol mixture 483 is cooled and pressure-controlled and then is led back to the inlet of the second rectifying tower 61 for circulation separation.
The reaction system and the method for preparing the methyl propionate greatly improve the conversion rate of the methyl propionate, can reach the complete conversion rate of more than 99.9 percent, can reach the purity of more than 99 percent, are beneficial to the full utilization of resources and can realize large-scale industrial production.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The reaction system for preparing methyl propionate is characterized by comprising a carbonyl esterification reaction device (1), an evaporator (2) and a first rectifying tower (3) which are sequentially communicated;
the evaporator (2) comprises a first output port and a second output port, the first output port is communicated with the feed inlet of the carbonyl esterification reaction device (1), and the second output port is communicated with the feed inlet of the first rectifying tower (3);
the carbonyl esterification reaction device (1) comprises a first stirring reaction kettle (11), a super-gravity rotating bed reactor (12) and a second stirring reaction kettle (13) which are sequentially communicated, wherein a discharge port of the second stirring reaction kettle (13) is communicated with a feed port of the evaporator (2).
2. The reaction system for preparing methyl propionate according to claim 1, characterized in that the reaction system further comprises a raw material purification device (5), wherein the discharge port of the raw material purification device (5) is communicated with the feed port of the carbonyl esterification reaction device (1).
3. The reaction system for producing methyl propionate according to claim 1, characterized in that the reaction system further comprises a pressure swing rectification apparatus (6); the pressure swing rectifying device (6) comprises a second rectifying tower (61), a discharge port at the top of the first rectifying tower (3) is communicated with a feed inlet of the second rectifying tower (61), and a discharge port at the bottom of the second rectifying tower (61) is communicated with a feed inlet of the carbonyl esterification reaction device (1).
4. A reaction system for producing methyl propionate according to claim 3, characterized in that the pressure swing rectification apparatus (6) further comprises a third rectification column (62); the discharge port of the top of the second rectifying tower (61) is communicated with the feed port of the third rectifying tower (62), and the discharge port of the top of the third rectifying tower (62) is communicated with the feed port of the second rectifying tower (61).
5. A process for the preparation of methyl propionate comprising the steps of:
s1: feeding ethylene (41), CO (42) and first methanol (431) into a carbonyl esterification reaction device (1) for carbonyl esterification reaction, sequentially feeding the ethylene (41), CO (42) and first methanol (431) into a first stirring reaction kettle (11), a hypergravity rotating bed reactor (12) and a second stirring reaction kettle (13) for reaction, and obtaining a reaction mixture (44);
s2: introducing the reaction mixture (44) obtained in the step 1 into an evaporator (2) for separation, and separating the reaction mixture (44) by the evaporator (2) to obtain a liquid-phase product (45) and a gas-phase product (46);
s3: the liquid phase product (45) at the bottom of the evaporator (2) is pressurized to return to the carbonyl esterification reaction device (1) for cyclic reaction after the catalyst is supplemented; condensing a gas-phase product (46) at the top of the evaporator (2), and introducing the condensed gas-phase product into a rectification system for separation to obtain methyl propionate and second methanol (432);
s4: and (3) pressurizing the second methanol (432) obtained in the step (3) back to the carbonyl esterification reaction device (1) for cyclic reaction.
6. The method for producing methyl propionate according to claim 5, wherein the evaporator (2) is provided as a falling film evaporator; the operation pressure of the falling film evaporator is 0.1MPa-0.3MPa, and the operation temperature is 65-105 ℃.
7. The method for producing methyl propionate according to claim 5, wherein raw material ethylene, raw material CO and raw material methanol are fed into a raw material purifying device (5) and purified, sulfur and chlorine impurities in the raw material ethylene and raw material CO are removed, and the raw material methanol is deoxidized; ethylene (41), CO (42) and first methanol (431) generated after purification are conveyed to the carbonyl esterification reaction device (1) and reacted.
8. The method for producing methyl propionate according to claim 5, wherein the rectification system comprises a first rectification column (3), the gaseous product (46) being introduced into the first rectification column (3) after condensation; the operation pressure of the top of the first rectifying tower (3) is 1-1.5 bar, the reflux ratio is 2-4, the gas-phase product (46) is separated by the first rectifying tower (3) to obtain first methyl propionate (471) and a first methyl propionate-methanol mixture (481), and the first methyl propionate (471) is discharged from a discharge hole at the bottom of the first rectifying tower (3).
9. The method for preparing methyl propionate according to claim 8, wherein the rectification system further comprises a pressure swing rectification device (6), the pressure swing rectification device (6) comprises a second rectification column (61), the first methyl propionate-methanol mixture (481) is discharged from a discharge port at the top of the first rectification column (3), and enters the second rectification column (61) after condensation; the top operating pressure of the second rectifying tower (61) is 1bar, the reflux ratio is 2-4, the second rectifying tower (61) separates the first methyl propionate-methanol mixture (481) to obtain second methanol (432) and a second methyl propionate-methanol mixture (482), and the second methanol (432) is discharged from a discharge hole at the bottom of the second rectifying tower (61) and enters the carbonyl esterification reaction device (1).
10. The method for preparing methyl propionate according to claim 9, wherein the pressure swing rectification apparatus (6) further comprises a third rectification column (62), the second methyl propionate-methanol mixture (482) is discharged from a discharge port at the top of the second rectification column (61), and enters the third rectification column (62) after being condensed; the operating pressure at the top of the third rectifying tower (62) is 6bar, the reflux ratio is 2-4, the third rectifying tower (62) separates the second methyl propionate-methanol mixture (482) to obtain a second methyl propionate (472) and a third methyl propionate-methanol mixture (483), and the second methyl propionate (472) is discharged from a discharge port at the bottom of the third rectifying tower (62); the third methyl propionate-methanol mixture (483) is discharged from a discharge hole at the top of the third rectifying tower (62) and enters the second rectifying tower (61).
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