CN115282913A - Reaction system and method for preparing methyl propionate - Google Patents
Reaction system and method for preparing methyl propionate Download PDFInfo
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- CN115282913A CN115282913A CN202210970158.6A CN202210970158A CN115282913A CN 115282913 A CN115282913 A CN 115282913A CN 202210970158 A CN202210970158 A CN 202210970158A CN 115282913 A CN115282913 A CN 115282913A
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- methyl propionate
- methanol
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 91
- 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 184
- 238000005886 esterification reaction Methods 0.000 claims abstract description 62
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 60
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 47
- SICCRERQCOIGDC-UHFFFAOYSA-N methanol;methyl propanoate Chemical compound OC.CCC(=O)OC SICCRERQCOIGDC-UHFFFAOYSA-N 0.000 claims description 37
- 239000012071 phase Substances 0.000 claims description 26
- 239000011541 reaction mixture Substances 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000011552 falling film Substances 0.000 claims description 8
- 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
- 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 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 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
- 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000005810 carbonylation reaction Methods 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
- 239000003205 fragrance Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint 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
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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 reaction kettle with stirring, a super-gravity rotary bed reactor and a second reaction kettle with stirring which are sequentially communicated. When the reaction system works, ethylene, CO and first methanol sequentially enter the first stirring reaction kettle, the supergravity rotary 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 with a chemical formula of C4H8O2, is a colorless transparent liquid, is slightly soluble in water, and is miscible in ethanol and diethyl ether. Are frequently used as solvents for cellulose nitrates, nitro lacquers, paints, varnishes, etc., as solvents for fragrances and flavorings, and also as intermediates in organic syntheses, such as the further condensation with formaldehyde to produce methyl methacrylate. At present, research on the production of methyl propionate by using ethylene as a raw material through a carbonyl esterification reaction has made a certain breakthrough, but the existing reaction conditions for synthesizing methyl propionate by homogeneous-phase hydrogen esterification of ethylene 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 preparing methyl propionate by using ethylene as a raw material and realize large-scale industrial application is a technical problem to be solved by many researchers at present.
Disclosure of Invention
The invention aims to provide a reaction system for preparing methyl propionate, which aims to solve the technical problems that the conversion rate of preparing methyl propionate by using ethylene as a raw material is low and large-scale industrial application cannot be realized in the prior art.
In order to achieve the purpose, the 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 supergravity rotary 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 also comprises a raw material purification device, and a discharge hole of the raw material purification device is communicated with a feed inlet of the carbonyl esterification reaction device.
Further, the reaction system further comprises a pressure swing rectifying device, the pressure swing rectifying device comprises a second rectifying tower, a discharge hole in the top of the first rectifying tower is communicated with a feed inlet of the second rectifying tower, and a discharge hole in 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; and the discharge hole at the top of the second rectifying tower is communicated with the feed inlet of the third rectifying tower, and the discharge hole at the top of the third rectifying tower is communicated with the feed inlet 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 using ethylene as a raw material is low and large-scale industrial application cannot be realized in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing methyl propionate comprising the steps of:
s1: feeding ethylene, CO and first methanol into a carbonyl esterification reaction device for carbonyl esterification reaction, and feeding the ethylene, the CO and the first methanol into a first stirred tank reactor, a super-gravity rotary bed reactor and a second stirred tank reactor in sequence for reaction to obtain a reaction mixture;
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 and returned to the carbonyl esterification reaction device for circular reaction after the catalyst is supplemented; introducing a gas-phase product at the top of the evaporator into a rectification system for separation after condensation to obtain methyl propionate and a second methanol;
s4: and (4) pressurizing the second methanol obtained in the step (3) to return to the carbonyl esterification reaction device for circular reaction.
Further, the evaporator is provided as a falling film evaporator; the operating pressure of the falling-film evaporator is 0.1MPa-0.3MPa, and the operating temperature is 65-105 ℃.
Further, feeding raw material ethylene, raw material CO and raw material methanol into a raw material purification device for purification, removing sulfur and chlorine impurities from the raw material ethylene and the raw material CO, and deoxidizing the raw material methanol; and conveying the ethylene, CO and the first methanol generated after 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 operating pressure at the top of the first rectifying tower is 1-1.5 bar, the reflux ratio is 2-4, the first rectifying tower separates the gas-phase product to obtain a mixture of first methyl propionate and first methyl propionate-methanol, 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 swing rectification device, the pressure swing rectification device comprises a second rectification tower, and the first methyl propionate-methanol mixture is discharged from a discharge hole in 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 a 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 distillation device also comprises a third distillation tower, wherein the second methyl dipropionate-methanol mixture is discharged from a discharge hole at the top of the second distillation tower and enters the third distillation tower after being condensed; the operation 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 hole at the bottom of the third rectifying tower; and discharging the third methyl tripropionate-methanol mixture from a discharge hole at the top of the third rectifying tower and feeding the third methyl tripropionate-methanol mixture into 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 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 reaction kettle with stirring, a super-gravity rotary bed reactor and a second reaction kettle with stirring which are sequentially communicated. When the reaction system works, ethylene, CO and first methanol enter a carbonyl esterification reaction device, sequentially enter a first stirring reaction kettle, a supergravity rotating bed reactor and a second stirring reaction kettle to carry out carbonyl esterification reaction, and release reaction heat while generating methyl propionate to obtain a reaction mixture; discharging the reaction mixture from the carbonyl esterification reaction device and feeding the reaction mixture into 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 and entering a carbonyl esterification reaction device for cyclic utilization, discharging the gas-phase product from a second output port, condensing by a condenser and then entering a first rectifying tower; and the first rectifying tower is used for separating the condensed gas-phase product to obtain first methyl propionate and a first methyl propionate-methanol mixture.
In the embodiment, the first stirring reaction kettle, the supergravity rotary 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 perform the carbonyl esterification reaction, and the conversion rate of methyl propionate is greatly improved; only 1 hypergravity rotary bed reactor is used in 3 reactors and is arranged between a first stirred tank reactor and a second stirred tank reactor, so that on one hand, the conversion rate is improved, and simultaneously, the operation cost is saved, and on the other hand, the excessive violent rotary bed reactor can be prevented from being placed at the head of a series connection to cause the excessive violent reaction heat release; the second stirred tank reactor mainly plays a role in stabilizing gas-liquid phases except for reaction, so that a reaction mixture discharged from the high-gravity rotating bed reactor can stably enter the evaporator. In addition, the liquid phase product obtained by the separation of the evaporator enters a carbonyl esterification reaction device for recycling, so that the cost is saved, and the conversion rate of methyl propionate is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a reaction system for preparing 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, which includes a plurality of rectifying towers according to an embodiment of the present invention.
Icon:
1-carbonyl esterification reaction device; 11-a first stirred tank reactor; 12-a hypergravity rotating bed reactor; 13-a second reaction kettle with a stirrer;
2-an evaporator;
3-a first rectification column;
41-ethylene; 42-CO; 431-first methanol; 432-a second methanol; 44-the reaction mixture; 45-liquid phase product; 46-gas phase product; 471-first methyl propionate; 472-methyl second propionate; 481-first methyl propionate-methanol mixture; 482-second propionic acid methyl ester-methanol mixture; 483-methyl tripropionate-methanol mixture;
5-a raw material purification device;
6-a pressure swing rectification device; 61-a second rectification column; 62-a third rectification column;
7-a condenser;
8-pump.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that in the description of the present invention, the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, which are only for convenience of describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" 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 interpreted broadly, for example, they may be fixedly connected, detachably connected, or integrally connected; can be directly connected or connected through an intermediate medium; either mechanically or electrically. The specific meanings of the above terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
Example one
The embodiment provides a reaction system for preparing methyl propionate, and referring to fig. 1, the system comprises a carbonyl esterification reaction device 1, an evaporator 2 and a first rectifying tower 3 which are communicated in sequence; 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 supergravity rotary bed reactor 12 and a second stirring reaction kettle 13 which are sequentially communicated, and 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, sequentially enter a first stirred tank reactor 11, a supergravity rotating bed reactor 12 and a second stirred tank reactor 13, carry out carbonyl esterification reaction under the catalysis of a catalyst, and release reaction heat while generating methyl propionate to obtain a reaction mixture 44; the reaction mixture 44 is discharged from the carbonyl esterification reaction device 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 the pump 8 and enters the carbonyl esterification reaction device 1 for cyclic utilization, and the gas-phase product 46 is discharged from a second output port and enters the first rectifying tower 3 after being condensed by the condenser 7; the first rectifying column 3 separates the condensed gas-phase product 46 to obtain a first methyl propionate 471 at the bottom of the column and a first methyl propionate-methanol mixture 481 in an azeotropic state at the top of the column.
In the embodiment, the first stirring reaction kettle 11, the supergravity rotary bed reactor 12 and the second stirring reaction kettle 13 are arranged in series, so that ethylene 41, CO42 and the first methanol 431 entering the carbonyl esterification reaction device 1 can fully perform the carbonyl esterification reaction, and the conversion rate of methyl propionate is greatly improved; only 1 hypergravity rotary bed reactor 12 is used in 3 reactors and is arranged between the first stirred tank reactor 11 and the second stirred tank reactor 13, so that on one hand, the conversion rate is improved, and simultaneously, the operation cost is saved, and on the other hand, the phenomenon that the reaction heat release is too violent due to the fact that the hypergravity rotary bed reactor 12 is placed at the first position of series connection can be avoided; the second stirred tank reactor 13 mainly plays a role in stabilizing gas-liquid two phases in addition to the reaction, so that the reaction mixture discharged from the high-gravity rotary bed reactor 12 can stably enter the evaporator 2. In addition, the liquid-phase product 45 obtained by separation in the evaporator 2 enters the carbonyl esterification reaction device 1 for recycling, so that the cost is saved, and the conversion rate of methyl propionate is improved.
Optionally, since the main reaction is concentrated in the first stirred tank reactor 11 and the high-gravity rotary bed reactor 12, the first stirred tank reactor 11 and the high-gravity rotary bed reactor 12 are provided with an internal coil pipe heat extraction and an external circulation heat extraction; that is, the first stirred tank reactor 11 is set as a tank reactor with a stirring and outer circulation heat exchange and inner heat exchange coil of the reactor, the high-gravity rotary bed reactor 12 is set as a high-gravity rotary bed reactor with an outer circulation heat exchange and inner heat exchange coil, and the second stirred tank reactor 13 is set as a tank reactor with an inner heat exchange coil.
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 contained in the raw materials on the reaction effect and further improve the conversion rate of the reaction, the reaction system further comprises a raw material purification device 5, and a discharge port of the raw material purification device 5 is communicated with a feed port of the carbonyl esterification reaction device 1. Ethylene 41, CO42 and first methanol 431, which are generated after the raw material ethylene, raw material CO and raw material methanol are purified in the raw material purification apparatus, are sent to the carbonylation reaction apparatus 1 and reacted.
Referring to fig. 2, the reaction system further comprises a pressure swing rectifying device 6, the pressure swing rectifying device 6 comprises a second rectifying tower 61, a discharge hole at the top of the first rectifying tower 3 is communicated with a feed inlet of the second rectifying tower 61, and a discharge hole at the bottom of the second rectifying tower 61 is communicated with a feed inlet of the carbonyl esterification reaction device 1.
When the reaction system works, a first methyl propionate-methanol mixture 481 is discharged from a discharge hole at the top of the first rectifying tower 3, is driven by a pump 8, and enters a pressure swing rectifying device 6 after being condensed; the first methyl propionate-methanol mixture 481 firstly enters a second rectifying tower 61, the second rectifying tower 61 separates the first methyl propionate-methanol mixture 481, a second methanol 432 with the purity of more than 99% is obtained at the bottom of the tower, and the second methanol 432 is discharged from a discharge hole at the bottom of the second rectifying tower 61 and enters a carbonyl esterification reaction device 1 for recycling; the second methyl propionate-methanol mixture 482 is obtained as an azeotropic mixture at the top of the column. In this embodiment, the second rectifying tower 61 further separates the reaction mixture, and the separated methanol enters the carbonyl esterification apparatus 1 for recycling, so that the cost is saved and the conversion rate of methyl propionate is increased.
Further, the pressure swing rectification device 6 also comprises a third rectification tower 62; the discharge port at the top of the second rectifying tower 61 is communicated with the feed port of the third rectifying tower 62, and the discharge port at 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, a second methyl propionate-methanol mixture 482 is discharged from a discharge hole at the top of the second rectifying tower 61, condensed and then enters a third rectifying tower 62; the third rectifying tower 62 separates the second methyl propionate-methanol mixture 482 entering the third rectifying tower, so that the second methyl propionate 472 with the purity of more than 99 percent 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; and obtaining a methyl tripropionate-methanol mixture 483 in an azeotropic state at the tower top, discharging the methyl tripropionate-methanol mixture 483 from a discharge hole at the tower top of the third rectifying tower 62, condensing, and then entering the second rectifying tower 61 for cyclic separation.
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 constitute the pressure swing rectifying apparatus 6; when the device is used, most of methyl propionate is separated out by the first rectifying tower 3, so that the separation operation pressure of the subsequent pressure swing rectifying device 6 is relieved to the greatest extent; the pressure swing rectification device 6 is used for circularly purifying and separating the methyl propionate-methanol mixture discharged from the first rectification tower 3 for multiple times, and the generated methanol can be recycled, so that the conversion rate of the methyl propionate is improved, and the conversion rate of the methyl propionate can reach more than 99.9%.
Example two
Referring to fig. 1, this example provides a process for preparing methyl propionate, comprising the steps of:
s1: feeding ethylene 41, CO42 and first methanol 431 into a carbonyl esterification reaction device 1 for carbonyl esterification reaction, and feeding the ethylene 41, the CO42 and the first methanol 431 into a first stirred tank reactor 11, a supergravity rotating bed reactor 12 and a second stirred tank reactor 13 in sequence for reaction to obtain 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 and returned to the carbonyl esterification reaction device 1 for circular reaction after the catalyst is supplemented; a gas-phase product 46 at the top of the evaporator 2 is condensed and then introduced into a rectification system for separation to obtain methyl propionate and a second methanol 432;
s4: pressurizing the second methanol 432 obtained in the step 3 to return to the carbonyl esterification reaction device 1 for circulating reaction.
Further, raw material ethylene, raw material CO and raw material methanol are sent into a raw material purification device 5 to be purified, sulfur and chlorine impurities in the raw material ethylene and the raw material CO are removed, and the raw material methanol is deoxidized; the ethylene 41, CO42 and the first methanol 431 generated after the purification are sent to the carbonyl esterification reaction apparatus 1 and reacted.
Further, the evaporator 2 is provided as a falling film evaporator; the operating pressure of the falling film evaporator is 0.1MPa-0.3MPa, and the operating temperature is 65-105 ℃. Preferably, the operating pressure of the falling-film evaporator is between 0.25MPa and 0.3MPa, corresponding to an operating temperature of between 96 and 104 ℃.
Further, the mass flow rate of liquid phase production at the bottom of the gas collecting tank of the evaporator 2 is controlled to be 20-60% of the mass flow rate of gas phase production at the top. Preferably, the mass flow rate of liquid phase production at the bottom of the gas collection tank of the evaporator 2 is controlled to be 30-50% of the mass flow rate of gas phase production at the top.
Referring to fig. 2, the rectification system comprises a first rectification column 3, and a gas-phase product 46 is condensed and 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 first rectification column 3 is operated at a pressure of 1 to 1.3bar and at a reflux ratio of 2 to 3.
Further, the rectification system also comprises a variable-pressure rectification device 6; the pressure swing rectification device 6 comprises a second rectification tower 61, and a first methyl propionate-methanol mixture 481 is discharged from a discharge hole at the top of the first rectification tower 3 and enters the second rectification 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 a 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 distillation device 6 further comprises a third distillation tower 62, wherein the second methyl propionate-methanol mixture 482 is discharged from a discharge hole in the top of the second distillation tower 61, and enters the third distillation 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 a 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 hole at the bottom of the third rectifying tower 62; a methyl tripropionate-methanol mixture 483 was discharged from a discharge port at the top of the third rectifying column 62 and was introduced into the second rectifying column 61.
In the embodiment, the molar ratio of the raw materials of ethylene, CO and methanol is 1-1.5; the molar ratio of the reaction product methyl propionate to the methanol mixture is in the interval of 2. Aiming at the molar ratio of methyl propionate to methanol in a reaction product, designing a series process of 3 rectifying towers; 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 firstly separated out by the first rectifying tower 3, the pressure of the subsequent separation operation is reduced to the greatest extent, the methyl propionate-methanol azeotrope generated at the tower top of the first rectifying tower 3 enters a pressure-variable rectifying device consisting of subsequent double towers, the methyl propionate-methanol azeotrope is separated by adopting rectifying towers with different operation pressures, and methanol and methyl propionate with the purity of more than 99 percent are respectively obtained at the tower bottoms of the two towers.
Preferably, the molar ratio of the raw materials ethylene, CO and methanol is 1.2-1.5.
The method is illustrated below by means of specific examples:
raw materials are supplied to a 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 purification device 5, sulfur and chlorine compounds contained in the raw materials of ethylene and CO are removed, and a small amount of dissolved oxygen is removed from the raw material of methanol.
Leading ethylene 41, CO42 and first methanol 431 which are generated after purification and a liquid phase product 45 which is recycled and contains the catalyst into a carbonyl esterification reaction device 1 which is formed by connecting a first stirring reaction kettle 11, a super-gravity rotary 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 percent and the methyl propionate accounts for 73.46 percent (mole fraction, the same applies hereinafter); 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, methanol accounted for 33.43%, and methyl propionate accounted for 66.57%; in the liquid-phase product 45, methanol accounts for 10.15%, and methyl propionate accounts for 89.85%; the liquid phase product 45 is cooled, pressurized, supplemented with a small amount of catalyst and then circulated back to the carbonyl esterification reaction device 1 for cyclic utilization, and the gas phase product 46 enters a rectification system after being cooled.
The gas-phase product 46 enters the first rectifying tower 3 after being cooled; the operation pressure at the top of the first rectifying tower 3 is 1bar, and the operation reflux ratio is 2.4; after separation, the first methyl propionate 471 at 0.3669kmol/h is obtained at the bottom of the tower, and the purity is more than or equal to 99.9%; a first methyl propionate-methanol mixture 481 of 0.38kmol/h in an azeotropic state is extracted from the top of the column, wherein the methyl propionate accounts for 65.61% and the methanol accounts for 34.39%.
The first methyl propionate-methanol mixture 481 is condensed and then introduced into the second rectification column 61; the operation pressure at the top of the second rectifying tower 61 is 1bar, and the reflux ratio is 2; after separation, 0.2483kmol/h of second methanol 432 is obtained at the bottom of the tower, the purity is more than or equal to 99.3 percent, and the second methanol 432 is introduced into the carbonyl esterification reaction device 1 for recycling; a second methyl propionate-methanol mixture 482 with a concentration of 1.0371kmol/h in an azeotropic state was taken out from the top of the column, wherein the methyl propionate accounted for 70.98% and the methanol accounted for 29.02%.
The second methyl propionate-methanol mixture 482 is pressurized and then continuously introduced into the third rectifying tower 62; the operation pressure at the top of the third rectifying tower 62 is 6bar, and the reflux ratio is 2; after separation, methyl propionate 0.1291kmol/h with purity not less than 99.3% is obtained at the bottom of the tower; 0.9081kmol/h of methyl tripropionate-methanol mixture 483 in an azeotropic state is obtained at the tower top, wherein the methyl propionate accounts for 80.97 percent, and the methanol accounts for 19.03 percent; the methyl tripropionate-methanol mixture 483 is cooled and pressure-controlled, and then is introduced back to the inlet of the second rectifying column 61 for cyclic separation.
The reaction system and the method for preparing methyl propionate provided by the invention greatly improve the conversion rate of methyl propionate, can reach the complete conversion rate of more than 99.9%, and the purity of methyl propionate can reach more than 99%, thereby being beneficial to the full utilization of resources and realizing large-scale industrial production.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The reaction system for preparing the methyl propionate is characterized by comprising a carbonyl esterification reaction device (1), an evaporator (2) and a first rectifying tower (3) which are communicated in sequence;
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 supergravity 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).
2. The reaction system for preparing methyl propionate according to claim 1, wherein the reaction system further comprises a raw material purification device (5), and a discharge port of the raw material purification device (5) is communicated with a feed port of the carbonyl esterification reaction device (1).
3. The reaction system for preparing methyl propionate according to claim 1, wherein the reaction system further comprises a pressure swing distillation device (6); the pressure swing rectification device (6) comprises a second rectification tower (61), a discharge hole in the top of the first rectification tower (3) is communicated with a feed inlet of the second rectification tower (61), and a discharge hole in the bottom of the second rectification tower (61) is communicated with a feed inlet of the carbonyl esterification reaction device (1).
4. The reaction system for preparing methyl propionate according to claim 3, wherein the pressure swing distillation device (6) further comprises a third distillation column (62); the discharge gate at second rectifying column (61) top of the tower communicate in the feed inlet of third rectifying column (62), the discharge gate at third rectifying column (62) top of the tower communicate in the feed inlet of second rectifying column (61).
5. A process for preparing 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, and feeding the ethylene (41), the CO (42) and the first methanol (431) into a first stirring reaction kettle (11), a supergravity rotating bed reactor (12) and a second stirring reaction kettle (13) in sequence for reaction to obtain 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 and returned to the carbonyl esterification reaction device (1) for circular reaction after the catalyst is supplemented; a gas-phase product (46) at the top of the evaporator (2) is condensed and then introduced into a rectification system for separation to obtain methyl propionate and a 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 circulating reaction.
6. The process for preparing methyl propionate according to claim 5, characterized in that the evaporator (2) is provided as a falling-film evaporator; the operating pressure of the falling film evaporator is 0.1MPa-0.3MPa, and the operating temperature is 65-105 ℃.
7. The method for preparing methyl propionate as set forth in claim 5, wherein the raw material ethylene, the raw material CO and the raw material methanol are fed to a raw material purification device (5) and purified, sulfur and chlorine impurities in the raw material ethylene and the raw material CO are removed, and the raw material methanol is deoxidized; the ethylene (41), CO (42) and first methanol (431) produced after the purification are sent to the carbonyl esterification reaction apparatus (1) and reacted.
8. The process for the preparation of methyl propionate according to claim 5 wherein the rectification system comprises a first rectification column (3), the gaseous products (46) being condensed and 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, 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), 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), and 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 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 a 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 distillation device (6) further comprises a third distillation column (62), and the second methyl propionate-methanol mixture (482) is discharged from a discharge port at the top of the second distillation column (61), and enters the third distillation column (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 hole at the bottom of the third rectifying tower (62); the third methyl tripropionate-methanol mixture (483) is discharged from a discharge port at the top of the third rectifying tower (62) and enters the second rectifying tower (61).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116099455A (en) * | 2023-04-12 | 2023-05-12 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649716A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN104529765A (en) * | 2014-12-18 | 2015-04-22 | 西南化工研究设计院有限公司 | Reaction device and method for producing methyl propionate |
| CN104804038A (en) * | 2014-01-23 | 2015-07-29 | 北京化工大学苏州（相城）研究院 | Phosphate ester preparation method |
| CN109053412A (en) * | 2018-08-13 | 2018-12-21 | 南京塔川化工设备有限公司 | Homogeneous premixing method before a kind of PTA energy saving device and CTA oxidation reaction |
| CN212335079U (en) * | 2020-05-09 | 2021-01-12 | 江苏湖大化工科技有限公司 | Production process device for synthesizing methyl methacrylate by methyl acetate and formaldehyde |
| CN112371072A (en) * | 2020-11-05 | 2021-02-19 | 浙江迪邦化工有限公司 | System and process for continuously producing diazonium salt solution |
| CN113731320A (en) * | 2021-09-30 | 2021-12-03 | 沈阳工业大学 | Dimethyl carbonate production device and method based on resource utilization |
-
2022
- 2022-08-12 CN CN202210970158.6A patent/CN115282913B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649716A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN104804038A (en) * | 2014-01-23 | 2015-07-29 | 北京化工大学苏州（相城）研究院 | Phosphate ester preparation method |
| CN104529765A (en) * | 2014-12-18 | 2015-04-22 | 西南化工研究设计院有限公司 | Reaction device and method for producing methyl propionate |
| CN109053412A (en) * | 2018-08-13 | 2018-12-21 | 南京塔川化工设备有限公司 | Homogeneous premixing method before a kind of PTA energy saving device and CTA oxidation reaction |
| CN212335079U (en) * | 2020-05-09 | 2021-01-12 | 江苏湖大化工科技有限公司 | Production process device for synthesizing methyl methacrylate by methyl acetate and formaldehyde |
| CN112371072A (en) * | 2020-11-05 | 2021-02-19 | 浙江迪邦化工有限公司 | System and process for continuously producing diazonium salt solution |
| CN113731320A (en) * | 2021-09-30 | 2021-12-03 | 沈阳工业大学 | Dimethyl carbonate production device and method based on resource utilization |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116099455A (en) * | 2023-04-12 | 2023-05-12 | 西南化工研究设计院有限公司 | Carbonylation reaction system and method based on multi-kettle serial connection |
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