CN114163328A - Co-production process method for synthesizing polyesters such as methyl propionate and alcohol by using methanol and CO - Google Patents
Co-production process method for synthesizing polyesters such as methyl propionate and alcohol by using methanol and CO Download PDFInfo
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- CN114163328A CN114163328A CN202111534097.0A CN202111534097A CN114163328A CN 114163328 A CN114163328 A CN 114163328A CN 202111534097 A CN202111534097 A CN 202111534097A CN 114163328 A CN114163328 A CN 114163328A
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- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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Abstract
The invention discloses a CO-production process method for synthesizing polyesters such as methyl propionate and alcohol by using methanol and CO, which comprises the following steps: carrying out carbonylation reaction on the reducing alcohol obtained by the system and the raw material CO in a carbonylation reaction kettle to obtain a product containing acetic acid; the product containing acetic acid is sent into a side plate reaction rectifying tower after flash evaporation separation, and is subjected to esterification reaction with raw material methanol sent from the bottom in the side plate reaction rectifying tower; and carrying out hydrogenation reaction on the gas-phase light component product of the esterification reaction in the side plate reaction rectifying tower to obtain reducing alcohol, circularly sending the reducing alcohol back to the carbonylation reaction kettle to participate in the carbonylation reaction, and extracting a target product containing methyl propionate and methanol in the side plate reaction rectifying tower. The invention realizes the synthesis of methyl propionate and alcohol only by using cheap methanol and CO as raw materials, and obtains the CO-production of methyl propionate, alcohol, methyl butyrate and other polyesters with low cost by using an efficient heat recovery technology.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a production process device and a production method of Methyl Methacrylate (MMA).
Background
The prior preparation process of methyl propionate comprises two steps: the process of coproducing propionate in the process of synthesizing propionic acid, the process of synthesizing methyl propionate by direct catalytic esterification, or the process of directly purchasing methyl propionate products synthesized from propionic acid raw materials has low economical efficiency. The process of synthesizing propionic acid is divided into two types, as follows:
one is that the ethylene hydroesterification process can be used for producing propionate, and the propionate can be hydrolyzed to obtain propionic acid;
CH 2=CH 2+CO+CH 3 OH— catalyst and process for preparing same →C 2 H 5 COOCH 3
The other is that the propionic acid is synthesized by carbonylation reaction mainly comprising methanol and ethanol, and then the propionic acid is esterified to become methyl propionate;
CO+CH 3 CH 2 OH— catalyst and process for preparing same →CH 3 CH 2 COOH
The ethylene capacity distribution in China is uneven, the ethylene capacity distribution is mainly in coastal areas in the east, the ethylene is inconvenient to transport for a long distance, and the transportation mode is that the ethylene is directly transported to a downstream plant device by a pipeline. The first approach, relying solely on ethylene to produce propionic acid and propionate esters, fails to meet the needs of the western inland region for propionic acid and propionate ester products. Meanwhile, the coal chemical industry in China has a large amount of methanol and is low in cost.
The traditional process is direct catalytic esterification to synthesize methyl propionate, as shown in figure 1. Propionic acid and methanol are added into a reaction kettle, methyl propionate is synthesized under the action of a catalyst and then enters a rectifying tower for separation, a mixture of propionic acid and water is obtained at the tower bottom, a mixture of methyl propionate, methanol and water is obtained at the tower top and then enters an extraction tower, an extracting agent (a mixture of polyhydric alcohol and water) is added into the extraction tower for extraction, so that high-purity methyl propionate is obtained, extraction liquid at the tower bottom enters a decompression tower for treatment, and the extracting agent prepared from the polyhydric alcohol and the water can be recycled. And separating the product in the bottom of the rectifying tower in a recovery tower to recycle the propionic acid.
The process has the advantages of complex reaction flow, high equipment investment, increased raw material investment due to the use of the extracting agent, increased energy consumption, and high production cost of the methyl propionate due to the fact that the raw material acid and the methyl propionate and other products are mixed together and need to be separated.
The prior art CN112851507A also discloses a process for synthesizing methyl methacrylate from ethanol, which comprises using ethanol and CO as raw materials, synthesizing propionic acid by carbonylation reaction under the action of a catalyst, then synthesizing methyl propionate by catalytic esterification with methanol, and finally performing gas-phase aldol condensation with formaldehyde to obtain MMA. The method adopts ethanol and CO as raw materials, so that methanol with low price cannot be used as the raw material, and meanwhile, the methyl propionate-containing product obtained after propionic acid esterification in the method also contains other acids, alcohols and alcohols, so that the yield of the subsequent aldol condensation reaction is reduced, and especially the heat energy of high-temperature and high-pressure gas after flash separation is not fully utilized, so that the MMA product cost is also increased. Moreover, the presence of water, a by-product of the aldol condensation and esterification reaction, is detrimental to the forward progress of the reaction, and no good solution is proposed in this technique for the separation of water, a by-product, which may lead to a reduction in the purity of MMA, a product and an increase in the cost.
Disclosure of Invention
The purpose of the invention is as follows: in view of the above existing problems and disadvantages, the present invention aims to provide a CO-production process for synthesizing polyesters such as methyl propionate and the like and alcohols from methanol and CO, which realizes the synthesis of methyl propionate and alcohols from cheap methanol and CO, and obtains the CO-production of methyl propionate and alcohols, and polyesters such as methyl butyrate and the like at low cost by using efficient heat energy recovery technology.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme: a CO-production process method for synthesizing polyesters such as methyl propionate and the like and alcohol by using methanol and CO comprises the following steps:
step S1, carrying out carbonylation reaction on the reduced alcohol obtained by the system and the raw material CO in a carbonylation reaction kettle to obtain a product containing acetic acid (generally containing acetic acid, propionic acid and butyric acid);
step S2, the product containing acetic acid is sent into a side plate reaction rectifying tower after flash evaporation separation, and is subjected to esterification reaction with raw material methanol sent from the bottom in the side plate reaction rectifying tower;
step S3, carrying out hydrogenation reaction on a gas-phase light component product of the esterification reaction in the side plate reaction rectifying tower to obtain reducing alcohol, and circularly feeding the reducing alcohol back to the carbonylation reaction kettle to participate in the carbonylation reaction;
and step S4, extracting target products containing methyl propionate and methanol from the side plate reactive distillation tower. The target product mainly comprises methyl propionate, methyl butyrate, ethyl butyrate and methanol, and ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and the like can be obtained from the target product through ester exchange.
Furthermore, a reaction separation plate for dividing the inner space of the side plate reaction rectifying tower into a reaction area and a product extraction area is arranged in the side plate reaction rectifying tower, and the feed inlets of the product containing acetic acid and the raw material methanol are both positioned on one side of the reaction area.
The reaction isolation plate is vertically arranged and divides the inner space of the side plate reaction rectifying tower into a reaction area and a product extraction area, and after a gas phase light component (containing an azeotrope of unreacted acid, alcohol and water) of the esterification reaction rises, two paths are provided: (1) in the liquid phase obtained by condensation after being extracted, the ester phase is sent back to the reaction rectifying tower, and the water phase is discharged; the gas phase component which is not condensed into the liquid phase is mainly azeotrope of methyl acetate, methanol and water, and is sent to the hydrogenation reactor for reduction to obtain reduced alcohol; (2) directly carrying out hydrogenation reaction by a hydrogenation reactor, and circularly returning the obtained reducing alcohol to the carbonylation reaction kettle to participate in the reaction; and the liquid phase product of the esterification reaction (mainly comprising methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate and a small amount of methanol and water) enters a product extraction zone from the bottom of the tower bottom, and is extracted according to needs, and acid (mainly comprising acetic acid, propionic acid and butyric acid) directly rises along with gas phase components in the process, so that the subsequent separation and purification processes of methyl propionate are reduced.
Furthermore, a hydrogenation reactor is coupled to the top of the side plate reaction rectifying tower, and a gas-phase light component product in the side plate reaction rectifying tower can directly enter the hydrogenation reactor from the top of the tower to participate in hydrogenation reaction. The reaction can obtain a mixture of methanol, ethanol and propanol.
Further, the product obtained after the flash separation in the step S2 is condensed and enters a liquid separation tank, the uncondensed gas-phase alcohol returns to the carbonylation reaction kettle to participate in the reaction, and the condensed liquid phase is sent to the side-plate reaction rectifying tower.
Further, the light components extracted from the top of the side-plate reactive rectifying tower in the step S3 enter a phase-splitting tank after being condensed, ester phases in a condensed liquid phase completely reflux to the side-plate reactive rectifying tower, and a water phase in the liquid phase is extracted; the condensed gas phase comprising acid, methanol and water is sent to the hydrogenation reactor.
Further, in the step S3, the reduced alcohol is partially sent back to participate in the carbonylation reaction, and is partially sent back to the side-plate reaction rectifying tower to participate in the esterification reaction.
Furthermore, the reaction zone in the side plate reaction rectifying tower leads out reaction materials through a lateral pipeline and sends the reaction materials into the reactor to carry out in-vitro knapsack reaction and then flows back to the side plate reaction rectifying tower.
Further, the extraction temperature of the target products of methyl propionate and methanol is 60-65 ℃; the extraction temperature of the methyl butyrate target product is 100-105 ℃.
Further, the high-temperature and high-pressure product subjected to flash separation in the step S2 is cooled and then sent to a liquid separation tank, and a liquid phase in the liquid separation tank is used as a cooling medium to cool the high-temperature and high-pressure product subjected to flash separation before being sent to the side plate reaction rectifying tower.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the process adopts cheap and easily available methanol as raw materials, and can realize co-production with formaldehyde industry. Methanol can be prepared from carbon dioxide and hydrogen, is a main basic raw material for carbon neutralization in the future, and green chemical products are mainly synthesized from methanol. The methyl propionate and methanol azeotropic product and other organic acid ester and methanol azeotropic products can be obtained in the coupling section of the subsequent reaction rectification and hydrogenation reaction.
2. Due to the mutual influence of the reaction process and the rectification operation, the reactive rectification has the advantages of the reactive rectification, and the reactive rectification comprises the following points:
a) the conversion rate and the selectivity of reactants are improved
For reversible reaction, the rectification operation removes the product generated by the reaction from the system, so that the reaction is continuously carried out in the positive reaction direction, and the limitation of the conversion rate by an equilibrium constant is broken, so that the reaction is more complete.
b) The chemical reaction process is stable and easy to control
The porosity in the tower is relatively high, liquid in the tower is uniformly distributed on the surface of the catalyst in the operation process and uniformly contacts with the gas phase, even if the reaction is a rapid exothermic reaction, the reaction heat can be transferred to the gas phase in time, and local 'temperature runaway' cannot be caused. The reaction temperature and the gas phase partial pressure in the catalytic distillation tower are controlled by the operation pressure of the tower, so that the influence of the temperature on the chemical reaction rate is reduced.
c) Reduce the investment cost and the operation cost of equipment and also reduce the energy consumption
The catalytic rectification technology combines the reaction and the rectification process, and the heat generated by the exothermic reaction can be directly used for generating steam in the tower, so that the reasonable utilization of the heat is realized; the organic acid-containing light component obtained by flash evaporation is subjected to condensation heat exchange with the organic acid-containing light component to realize heat recycling, so that energy and equipment investment are saved.
d) The reaction rectifying tower is internally provided with an external knapsack reactor, so that the equipment is compact, and the space occupied by the operation is reduced.
e) The reaction rectifying tower is provided with the isolation plate, so that the organic acid light component in the reaction area can not enter the extraction area, the subsequent product separation is avoided, and the difficulty brought to the rectifying separation operation by the formation of an azeotrope can be effectively avoided.
For some systems which are difficult to separate, such as the separation of an azeotrope system which is difficult to realize by the common method, the effective separation of the azeotrope system can be realized by adding an entrainer and the like in the rectification process.
f) For reactive distillation, the catalyst filling layer plays a role in accelerating the chemical reaction rate and mass transfer.
3. The method removes an extraction section, reduces the use of a solvent, is more environment-friendly in flow, and mainly comprises the steps of removing the non-condensable gas at the tower top and generating water through esterification reaction.
Drawings
FIG. 1 is a flow diagram of a process for the production of methyl propionate according to the prior art;
FIG. 2 is a process flow diagram of a CO-production process for synthesizing polyesters such as methyl propionate and alcohol from methanol and CO in accordance with the present invention.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
As shown in fig. 2, the process for synthesizing methyl propionate by using methanol and CO as raw materials according to the present invention is briefly introduced below, and mainly comprises a hydroxylation reaction section and an esterification reaction rectification and hydrogenation coupling section:
first, carbonylation reaction section
The reaction content is as follows:
main reaction-carbonylation reaction: CH (CH)3OH+CO→CH3COOH
Main reaction-carbonylation reaction: CH (CH)3CH2OH+CO→CH3CH2COOH, propanol, butanol and CO are subjected to carbonylation reaction to synthesize the corresponding acid.
Side reaction:
and (3) shift reaction: CO + H2O→CO2+H2
In the invention, in a carbonylation reactor (R101), carbon monoxide and methanol (the methanol can be fed in the carbonylation reactor R101 and/or a side plate reaction rectifying tower T103) are continuously reacted under a certain condition to generate acetic acid, and the carbon monoxide and ethanol generated in a hydrogenation working section at the top of the reaction rectifying tower are continuously reacted to generate propionic acid. The carbonylation reactor can carry out carbonylation reaction of mixed alcohol, and controls the reflux of hydrogenation reaction according to the process requirement, so that the carbonylation reactor can be a mixture of methanol and/or ethanol.
Catalyst system: the catalyst for carbonylation reaction includes active component, assistant and stabilizer. The active component is rhodium or iridium complex, the auxiliary agent is methyl iodide and ethyl iodide, and the stabilizing agent is alkali metal halide or formylmorpholine.
The process is briefly described as follows:
feeding: methanol and carbon monoxide
The process comprises the following steps: the operating temperature of the carbonylation reaction kettle R101 is 150-200 ℃, and the operating pressure is 2.5-3.5 MPa. In the reactor (R101) carbon monoxide and methanol/ethanol are continuously reacted to form acetic acid and/or propionic acid. The carbonylation reactor can carry out carbonylation of mixed alcohol, and hydrogenation reaction reflux is controlled according to the process requirement, so that the carbonylation reactor can be a mixture of methanol and/or ethanol. And (3) feeding the product containing acetic acid and/or propionic acid obtained in the carbonylation reaction into a flash tank S101 for flash evaporation. The heavy components in flash tank S101 are returned to carbonylation reactor R101 by pump P101. The light component goes to the condenser (E101) to carry out partial condensation, the condensing medium at the position adopts the liquid phase component at the bottom of the liquid separation tank, the heat of the liquid phase component can be fully utilized, after cooling, the liquid separation tank S102 carries out phase separation, the pressure of the liquid separation tank is controlled to be about 1MpaG, after liquid separation, the bottom liquid phase (mainly acetic acid and propionic acid) is taken as a cooling medium to cool the light component of the flash tank through a cooler E101A before being pressed into a reaction rectification section to carry out esterification reaction rectification, and when the cooling temperature does not meet the requirement, the light component can be cooled again through a secondary cooler E101B; the gas at the top of the liquid separating tank S102 is pressed into a carbonylation reaction kettle R101 by a booster fan F101; and (4) discharging the incompressible light component gas to a tail gas treatment system for absorption and incineration.
In the process, because the pressure of S101 is different from that of S102, the mixed acid (with higher pressure) at the outlet of S102 exchanges heat with the high-temperature gas at the inlet of S101, so that the aim of saving energy is fulfilled.
Second, reaction rectification hydrogenation coupling section
Catalytic rectification side main reaction
Esterification reaction: CH (CH)3CH2COOH+CH3OH→CH3CH2COOCH3
Esterification reaction: CH (CH)3COOH+CH3OH→CH3COOCH3
Top hydrogenation main reaction:
CH3COOCH3+2H2→CH3CH2OH+CH3OH
CH3CH2COOCH3+2H2→CH3CH2CH2OH+CH3OH and the like
Catalyst system: strong acid cation exchange resin
The process is briefly described as follows:
the reactive distillation column T101 adopts a partition column and hydrogenation reaction coupling design, namely: a side plate is vertically arranged in the reaction rectifying tower, and the internal space of the reaction rectifying tower is divided into a reaction area and a product extraction area; meanwhile, a hydrogenation reactor which is communicated and coupled with the reaction area is arranged at the top of the tower. The operating conditions in the reactive distillation column are as follows: normal pressure and operation temperature of about 62-110 ℃.
Propionic acid and acetic acid are fed at the upper part of the catalytic distillation reaction side A, and methanol is fed at the lower part of the catalytic distillation side A. Esterification reaction is carried out, and methyl acetate and methyl propionate are mainly generated. The side line is extracted by the pump P102 and is pumped back to the tower after further reaction in the backpack reactor R102, thereby improving the reaction efficiency and speed, reducing the height of the tower and reducing the occupied area.
The reaction rectifying tower catalyzes the heavy components such as methyl acetate and methyl propionate generated by the esterification reaction on the rectifying side A, methyl butyrate and/or ethyl butyrate and the like to flow down and enter a product extraction area on the other side, and the gas phase light component part directly enters a hydrogenation reactor to obtain corresponding alcohol and enters a condenser E102; meanwhile, light components at the top of the reactive distillation tower are partially extracted and condensed by a condenser E103, the condensing temperature is controlled to be about 62.5 ℃, condensate enters a phase separation tank S103, an ester phase is totally refluxed, and a water phase automatically flows to an inlet of a water extraction pump P105. E103 gas phase is mainly composed of azeotrope of methyl acetate, methanol and water, the gas phase reflows to enter a hydrogenation reactor R103 at the top of the reactive distillation tower to react to generate methanol, ethanol and the like, and finally the gas phase is condensed by a condenser E102 and enters a liquid separation tank S104, the liquid phase is pumped back to a carbonylation reaction kettle R101 by a pump P103, and the gas phase is sent to a tail gas treatment system to be absorbed and incinerated.
In the reactive distillation process, ester phase at the top of the tower is totally refluxed, and an azeotropic product of methyl propionate and methanol is extracted from a side line pump (P104); an azeotropic product of ethyl propionate and methanol is extracted from a side line pump P107, and the extraction temperature is 60-65 ℃; and (3) collecting methyl butyrate and ethyl butyrate products from a side line pump P108 at the temperature of 100-105 ℃. The water formed during the catalytic reaction is also taken off by the side stream by means of the pump P105. The tower bottom is mainly composed of organic acid, ester and other heavy components, and is discharged outwards by a pump P106.
The invention removes the product from the reaction system in time, which can break the original balance, promote the reaction to proceed forward, and improve the conversion rate of the reactant, compared with the traditional method, the conversion rate is 95%, and the conversion rate can be improved to 99.5% by the reactive distillation process. The process of reaction rectification and coupling hydrogenation of the isolation plate replaces the functions of a reaction kettle, a rectifying tower and a recovery tower in the traditional process, reduces the equipment investment, reduces the energy consumption by 60 percent, and simultaneously realizes the synthesis of the azeotropic product of the organic acid ester and the alcohol by only taking the easily obtained and cheap methanol and CO as raw materials.
It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
Claims (9)
1. A CO-production process method for synthesizing polyesters such as methyl propionate and the like and alcohol by using methanol and CO is characterized by comprising the following steps:
step S1, carrying out carbonylation reaction on the reducing alcohol obtained by the system and the raw material CO in a carbonylation reaction kettle to obtain a product containing acetic acid;
step S2, the product containing acetic acid is sent into a side plate reaction rectifying tower after flash evaporation separation, and is subjected to esterification reaction with raw material methanol sent from the bottom in the side plate reaction rectifying tower;
step S3, carrying out hydrogenation reaction on a gas-phase light component product of the esterification reaction in the side plate reaction rectifying tower to obtain reducing alcohol, and circularly feeding the reducing alcohol back to the carbonylation reaction kettle to participate in the carbonylation reaction;
and step S4, extracting target products containing methyl propionate and methanol from the side plate reactive distillation tower.
2. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: the side plate reaction rectifying tower is internally provided with a reaction isolation plate which divides the internal space of the side plate reaction rectifying tower into a reaction area and a product extraction area, and the feed inlets of the product containing acetic acid and the raw material methanol are positioned on one side of the reaction area.
3. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: the top of the side plate reaction rectifying tower is coupled with a hydrogenation reactor, and gas-phase light component products in the side plate reaction rectifying tower can directly enter the hydrogenation reactor from the top of the tower to participate in hydrogenation reaction.
4. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: and (4) condensing the product subjected to flash separation in the step S2, feeding the product into a liquid separation tank, returning the uncondensed gas-phase alcohol to the carbonylation reaction kettle for reaction, and feeding the condensed liquid phase into a side plate reaction rectifying tower.
5. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: condensing the light components extracted from the top of the side-plate reaction rectifying tower in the step S3, then feeding the condensed light components into a phase splitting tank, fully refluxing the ester phase in the condensed liquid phase to the side-plate reaction rectifying tower, and extracting the water phase in the liquid phase; the condensed gas phase comprising acid, methanol and water is sent to the hydrogenation reactor.
6. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: and in the step S3, part of the reduced alcohol is sent back to participate in the carbonylation reaction, and part of the reduced alcohol is sent back to the side plate reaction rectifying tower to participate in the esterification reaction.
7. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 2, wherein: and the reaction zone in the side plate reaction rectifying tower is used for leading out reaction materials through a lateral pipeline, sending the reaction materials into a reactor for in vitro knapsack reaction, and then refluxing the reaction materials to the side plate reaction rectifying tower.
8. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 2, wherein: the extraction temperature of the target products of methyl propionate and methanol is 60-65 ℃; the extraction temperature of the methyl butyrate target product is 100-105 ℃.
9. The CO-production process for synthesizing polyesters such as methyl propionate and alcohols from methanol and CO as claimed in claim 1, wherein: and (4) cooling the high-temperature and high-pressure product subjected to flash separation in the step S2, and then sending the product into a liquid separation tank, wherein the liquid phase in the liquid separation tank is used as a cooling medium to cool the high-temperature and high-pressure product subjected to flash separation before being sent into a side plate reaction rectifying tower.
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| PCT/CN2021/141261 WO2023108799A1 (en) | 2021-12-15 | 2022-09-06 | Co-production process method for synthesizing methyl propionate and other polyesters and alcohols from methanol and co |
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| 李建伟;刘思明;张香平;: "甲醇羰基合成甲基丙烯酸甲酯的模拟研究" * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023108799A1 (en) * | 2021-12-15 | 2023-06-22 | 江苏湖大化工科技有限公司 | Co-production process method for synthesizing methyl propionate and other polyesters and alcohols from methanol and co |
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| Publication number | Publication date |
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| WO2023108799A1 (en) | 2023-06-22 |
| CN114163328B (en) | 2023-10-03 |
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