CN116099455B - Carbonylation reaction system and method based on multi-kettle serial connection - Google Patents
Carbonylation reaction system and method based on multi-kettle serial connection Download PDFInfo
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Abstract
The invention discloses a carbonylation reaction system and a carbonylation reaction method based on multi-kettle serial connection, belongs to the technical field of chemical industry, and solves the technical problem that the requirements of reaction and separation and purification of methyl propionate prepared by ethylene carbonylation on kettle liquid composition are similar. The system comprises a reaction kettle A, a reaction kettle B connected with the reaction kettle A, an evaporator connected with the reaction kettle B, a rectifying tower connected with the evaporator, and a methyl propionate product output pipe connected with the rectifying tower kettle; the reaction kettle A is connected with a material conveying pipe. The method mainly comprises the steps of conveying raw materials to a reaction kettle A for rapid ethylene carbonylation reaction, and conveying the raw materials to a reaction kettle B for ethylene carbonylation reaction with improved methyl propionate content.
Description
Technical Field
The invention belongs to the technical field of chemical industry, relates to the technology of synthesizing organic chemical products by olefin carbonylation, and in particular relates to a carbonylation reaction system and method based on multi-kettle serial connection.
Background
Methyl Methacrylate (MMA) is a basic raw material of high-end materials such as aerospace, electronic information, optical fibers, optical lenses, robots and the like, and the production capacity of MMA in China exceeds 170 ten thousand tons/year by the end of 2021. In the prior art, the MMA industrial production method comprises an Acetone Cyanohydrin (ACH) method, an isobutene oxidation method, a C2 method and the like. The ACH method is mature, is always a main route of MMA production in China, and the total productivity in 2021 reaches 116 ten thousand tons/year, which accounts for 68% of the total productivity.
The ACH method was developed by the imperial chemical industry group (ICI) in the united kingdom and was industrialized in 1937. The method takes the highly toxic hydrocyanic acid and sulfuric acid as raw materials, and has high environmental protection pressure.
The isobutylene method was developed by the Japanese catalyst chemical industry company and Mitsubishi rayon company in 1982, and the isobutylene method was adopted for global production of MMA of more than 20%. The route has the advantages of long process flow, complex equipment, lower MMA total selectivity and higher investment and production cost.
The C2 MMA synthesis technology, a representative Lucite (cellulite) alpha-MMA technology, was developed by Shell (Shell). The route has mild process conditions, is safe and environment-friendly, and can save 40% of investment and production cost compared with the traditional route.
The process for synthesizing MMA by an ethylene route two-step method comprises the steps of preparing methyl propionate by ethylene carbonylation and preparing MMA by condensing methyl propionate with formaldehyde. The existing catalyst for synthesizing methyl propionate by ethylene carbonylation is mainly a transition metal complex, central metal is mainly Pd, rh, ni and other transition metals, ligands are mainly phosphine ligands such as alkyl phosphine, cycloalkyl phosphine, bidentate phosphine, multidentate phosphine and the like, and the reaction rate is improved by adding an acid accelerator. The catalyst system is dissolved in reaction liquid to accelerate the carbonylation reaction of ethylene, and the obtained homogeneous product liquid generally comprises methanol, methyl propionate, catalyst complex, dissolved trace ethylene, CO, acid auxiliary agent and the like.
In the prior art, few reports exist about the reaction device and the technology for preparing methyl propionate by ethylene carbonylation.
Patent CN102741213a discloses a continuous process for the carbonylation of CO with ethylene in the liquid phase in the presence of a CO-reactant having mobile hydrogen atoms and a suitable catalyst system. Patent CN201410797826a discloses a reaction device for producing methyl propionate, which comprises a static mixer, a carbonylation reactor and a flash evaporator which are connected in sequence, wherein the top of the flash evaporator is connected with a light component removal tower, and the bottom of the flash evaporator is connected with a catalyst recovery reactor; tail gas from the light component removal tower enters a tail gas treatment system after passing through a condenser, and the bottom of the light component removal tower is connected with a rectification refining system; the catalyst recovery reactor is connected with the liquid-liquid separation tower, the upper material separated by the liquid-liquid separation tower enters the tar incineration system, and the obtained heavy phase returns to the carbonylation reactor.
In the prior art, a part of light components (comprising methanol, methyl propionate and dissolved gas) in the product liquid are separated from the catalyst in a common evaporation mode, the evaporated light components are further separated to obtain a methyl propionate product, and the mother liquor containing the catalyst is recycled to the reactor. The distilled light component mainly consists of methyl propionate and methanol, the methyl propionate and the methanol are azeotroped (the azeotropic composition at normal pressure is about 50wt%:50 wt%) and the boiling points of the methyl propionate, the azeotrope and the methanol at normal pressure are 79.7 ℃ and 62 ℃ and 64.8 ℃ respectively, the methyl propionate is taken out from the tower kettle of a rectifying tower as high-boiling components, and for further separation to obtain a methyl propionate product, the content of the methyl propionate in the light component distilled in the evaporation process is generally required to be higher than the azeotropic composition, and the higher the content is, the lower the separation energy consumption is. Ethylene, CO and methanol are synthesized into methyl propionate under the action of a homogeneous catalyst, the reaction rate is closely related to the composition of a reaction liquid, the content of methyl propionate in the reaction liquid is increased, the content of raw material methanol is reduced, and the reaction rate is obviously reduced. Therefore, from the standpoint of product separation, the higher the methyl propionate content in the product liquid is, the more advantageous, but the higher the methyl propionate content will lead to a decrease in the reaction rate, which is disadvantageous in that the methyl propionate synthesis reaction in the process of producing methyl propionate by ethylene carbonylation and the separation and purification of methyl propionate from the reaction liquid are in demand for the components of the reaction liquid. Furthermore, as known from the carbonylation ligand disclosed in publication number CN105153241a and its use in carbonylating ethylenically unsaturated compounds, methanol and dissolved trace CO in the product liquid can induce the reduction of divalent palladium to zero-valent, resulting in precipitation of palladium metal and a decrease in catalyst activity during separation.
Disclosure of Invention
The invention aims to solve the technical problems that: a carbonylation reaction system and a carbonylation reaction method based on multi-kettle serial connection are provided, so as to at least solve part of the technical problems.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a carbonylation reaction system based on multi-kettle serial connection comprises a reaction kettle A, a reaction kettle B connected with the reaction kettle A, an evaporator connected with the reaction kettle B, a rectifying tower connected with the evaporator, and a methyl propionate product output pipe connected with the rectifying tower kettle; the reaction kettle A is connected with a material conveying pipe; the light phase outlet of the evaporator is connected with a cooler, the liquid phase material flow outlet of the cooler is connected with a rectifying tower, the evaporator is connected with the rectifying tower through the cooler, and the gas phase material flow outlet of the cooler is connected with a reaction kettle A.
Further, the reactor also comprises a gas-liquid separator connected from the reactor B, wherein a liquid phase outlet of the gas-liquid separator is connected to the evaporator, a gas phase outlet of the gas-liquid separator is connected to the reactor A, and the reactor B is connected to the evaporator through the gas-liquid separator.
Further, the reactor also comprises a reaction kettle C which is connected to the evaporator from a liquid phase outlet of the gas-liquid separator, and the liquid phase outlet of the gas-liquid separator is connected to the evaporator through the reaction kettle C.
Further, the heavy phase outlet of the evaporator is connected to a reaction kettle A, and the top of the rectifying tower is connected to the reaction kettle A through a pipeline;
the material conveying pipe comprises an ethylene conveying pipe, a methanol conveying pipe and a carbon monoxide conveying pipe.
Further, the reactor also comprises a mixer connected to the reaction kettle A, a conveying pipeline connected to the reaction kettle A and equipment except the evaporator are connected to the mixer first and connected to the reaction kettle A through the mixer.
A reaction method based on a multi-kettle serial carbonylation reaction system comprises the following steps:
step 2, conveying the product stream after the reaction in the reaction kettle A to the reaction kettle B to continue the ethylene carbonylation reaction;
and 4, sending the light phase separated from the evaporator into a rectifying tower for separation, and obtaining a methyl propionate product to be extracted from the bottom of the rectifying tower.
Further, in the step 1, the temperature of the ethylene carbonylation reaction of the raw materials of methanol, ethylene and CO is 60-150 ℃, the pressure is 5-30 bar, and the catalyst system in the reaction kettle A consists of palladium salt, phosphine ligand and cocatalyst;
in the step 3, a part of the heavy phase separated from the evaporator is sent to a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part is sent to the outside to recover the catalyst therein;
in the step 4, the enriched methanol at the top of the rectifying tower is extracted, one part of the methanol is sent into a mixer to be mixed with raw materials of methanol, ethylene and CO and then is sent into a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part of the methanol is sent and recovered.
Further, in the step 2, in the product stream after the reaction in the reaction kettle a, the gas and the liquid respectively enter the reaction kettle B to continue the ethylene carbonylation reaction, or the gas and the liquid enter the reaction kettle B together to continue the ethylene carbonylation reaction.
Further, in the step 3, the liquid phase of the product stream after the reaction in the reaction kettle B is separated by the gas-liquid separator and is conveyed to the reaction kettle C for continuous ethylene carbonylation reaction, and the product stream after the reaction in the reaction kettle C is conveyed to the evaporator for separation;
one part of the gas phase separated by the gas-liquid separator is sent to a mixer to be mixed with raw materials of methanol, ethylene and CO, and then is sent to a reaction kettle A to participate in ethylene carbonylation reaction, and the other part is sent to be recycled;
the mass content of methanol in the product liquid in the reaction kettle A is higher than 20%, and the mass content of methyl propionate in the product liquid in the reaction kettle B and the reaction kettle C is higher than 60%.
Further, in the step 4, the light phase separated from the evaporator is sent to a cooler for cooling, and the cooled liquid phase is sent to a rectifying tower for separation;
and (3) sending one part of the gas phase cooled by the cooler into a mixer to be mixed with raw materials of methanol, ethylene and CO, and sending the mixed gas phase into a reaction kettle A to participate in ethylene carbonylation reaction, and sending the other part of the gas phase to be recycled.
Compared with the prior art, the invention has the following beneficial effects:
the system has simple structure, scientific and reasonable design and convenient use, and the matched production process can effectively solve the technical problem that the methyl propionate synthesis reaction and the separation and purification of methyl propionate from the reaction liquid are about to the demands of the components of the reaction liquid in the process of preparing the methyl propionate by ethylene carbonylation.
The multi-kettle serial reaction system consists of a main reactor (reaction kettle A) and an auxiliary reactor (reaction kettle B and/or reaction kettle C), wherein the main reactor has higher methanol content and lower methyl propionate content, the reaction rate is high, and the ethylene carbonylation reaction mainly occurs in the main reactor; the product liquid of the main reactor is input into an auxiliary reactor for further reaction, and the main function of the auxiliary reactor is to improve the methyl propionate content in the reaction liquid so as to be beneficial to product separation. In addition, after the methanol and CO in the reaction liquid are further consumed in the auxiliary reactor, the reaction liquid is sent to a separation refining unit such as evaporation, rectification and the like, and the stability of the catalyst system is improved. The reaction and separation processes are more efficient, the methyl propionate synthesis and separation and purification cost can be effectively reduced, the technical competitiveness is enhanced, and the application prospect is good.
Drawings
FIG. 1 is a schematic diagram of a system according to the present invention.
FIG. 2 is a graph showing the change in the feed gas consumption rate with the reaction time in example 1.
FIG. 3 is a graph of the feed composition of the rectifying column versus the energy consumption of the rectifying separation in example 2.
Wherein, the names corresponding to the reference numerals are:
1-reaction kettle A, 2-reaction kettle B, 3-evaporator, 4-rectifying tower, 5-methyl propionate product external conveying pipe, 6-ethylene conveying pipe, 7-methanol conveying pipe, 8-carbon monoxide conveying pipe, 9-reaction kettle C, 10-gas-liquid separator, 11-cooler and 12-mixer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
As shown in fig. 1, the carbonylation reaction system based on multi-kettle serial connection provided by the invention comprises a reaction kettle A1, a reaction kettle B2 connected with the reaction kettle A1, an evaporator 3 connected with the reaction kettle B2, a rectifying tower 4 connected with the evaporator 3, and a methyl propionate product external conveying pipe 5 connected with the rectifying tower 4; the reaction kettle A1 is connected with a material conveying pipe; the light phase outlet of the evaporator 3 is connected with a cooler 11, the liquid phase material flow outlet of the cooler 11 is connected with the rectifying tower 4, the evaporator 3 is connected with the rectifying tower 4 through the cooler 11, and the gas phase material flow outlet of the cooler 11 is connected with the reaction kettle A1.
The invention also comprises a gas-liquid separator 10 connected from the reaction kettle B2, wherein a liquid phase outlet of the gas-liquid separator 10 is connected to the evaporator 3, a gas phase outlet of the gas-liquid separator is connected to the reaction kettle A1, and the reaction kettle B2 is connected to the evaporator 3 through the gas-liquid separator 10.
The invention also comprises a reaction kettle C9 which is connected to the evaporator 3 from the liquid phase outlet of the gas-liquid separator 10, wherein the liquid phase outlet of the gas-liquid separator 10 is connected to the evaporator 3 through the reaction kettle C9.
The heavy phase outlet of the evaporator 3 is connected to the reaction kettle A1, and the top of the rectifying tower 4 is connected to the reaction kettle A1 through a pipeline;
the material conveying pipe comprises an ethylene conveying pipe 6, a methanol conveying pipe 7 and a carbon monoxide conveying pipe 8.
The invention also comprises a mixer 12 connected to the reaction kettle A1, a conveying pipeline connected to the reaction kettle A1 and equipment except the evaporator 3 are connected to the mixer 12 first and connected to the reaction kettle A1 through the mixer 12.
The system has simple structure, scientific and reasonable design and convenient use, and the matched production process can effectively solve the technical problem that the methyl propionate synthesis reaction and the separation and purification of methyl propionate from the reaction liquid are about to the demands of the components of the reaction liquid in the process of preparing the methyl propionate by ethylene carbonylation.
The system comprises a mixer, a reaction kettle A, a reaction kettle B, a gas-liquid separator, a reaction kettle C, an evaporator, a cooler and a rectifying tower which are connected in sequence. The mixer is connected with the reaction kettle A through a pipeline, and the outlet of the reaction kettle A is connected to the reaction kettle B through a pipeline; a gas-liquid separator is arranged behind the reaction kettle B, a gas phase material flow outlet of the gas-liquid separator is connected to a mixer, and a liquid phase material flow outlet of the gas-liquid separator is connected to the reaction kettle C; the outlet of the reaction kettle C is connected to an evaporator, the heavy phase outlet of the evaporator is connected to a mixer, and the light phase outlet of the evaporator is connected to a cooler; the gas phase material flow outlet of the cooler is connected to the mixer, and the liquid phase material flow outlet is connected to the rectifying tower; the outlet of the material flow extracted from the top of the rectifying tower is connected to a mixer, and the methyl propionate product is extracted from the bottom of the rectifying tower.
The multi-kettle serial reaction system consists of a main reactor (reaction kettle A) and an auxiliary reactor (reaction kettle B and/or reaction kettle C), wherein the main reactor has higher methanol content and lower methyl propionate content, the reaction rate is high, and the ethylene carbonylation reaction mainly occurs in the main reactor; the product liquid of the main reactor is input into an auxiliary reactor for further reaction, and the main function of the auxiliary reactor is to improve the methyl propionate content in the reaction liquid so as to be beneficial to product separation. In addition, after the methanol and CO in the reaction liquid are further consumed in the auxiliary reactor, the reaction liquid is sent to a separation refining unit such as evaporation, rectification and the like, and the stability of the catalyst system is improved. The reaction and separation processes are more efficient, the methyl propionate synthesis and separation and purification cost can be effectively reduced, the technical competitiveness is enhanced, and the application prospect is good.
As shown in fig. 1, the invention also provides a reaction method based on a multi-kettle serial carbonylation reaction system, which comprises the following steps:
step 2, conveying the product stream after the reaction in the reaction kettle A to the reaction kettle B to continue the ethylene carbonylation reaction;
and 4, sending the light phase separated from the evaporator into a rectifying tower for separation, and obtaining a methyl propionate product to be extracted from the bottom of the rectifying tower.
In the step 1, the temperature of the ethylene carbonylation reaction of the raw materials of methanol, ethylene and CO is 60-150 ℃, the pressure is 5-30 bar, and a catalyst system in a reaction kettle A consists of palladium salt, phosphine ligand and cocatalyst; in the step 3, a part of the heavy phase separated from the evaporator is sent to a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part is sent to the outside to recover the catalyst therein; in the step 4, the enriched methanol at the top of the rectifying tower is extracted, one part of the methanol is sent into a mixer to be mixed with raw materials of methanol, ethylene and CO and then is sent into a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part of the methanol is sent and recovered.
In the step 2, in the product stream after the reaction in the reaction kettle A, gas and liquid enter the reaction kettle B respectively to continue the ethylene carbonylation reaction, or the gas and the liquid enter the reaction kettle B together to continue the ethylene carbonylation reaction.
In the step 3, the liquid phase of the product stream after the reaction in the reaction kettle B is separated by a gas-liquid separator and is conveyed to the reaction kettle C for continuous ethylene carbonylation reaction, and the product stream after the reaction in the reaction kettle C is conveyed to an evaporator for separation; one part of the gas phase separated by the gas-liquid separator is sent to a mixer to be mixed with raw materials of methanol, ethylene and CO, and then is sent to a reaction kettle A to participate in ethylene carbonylation reaction, and the other part is sent to be recycled; the mass content of methanol in the product liquid in the reaction kettle A is higher than 20%, and the mass content of methyl propionate in the product liquid in the reaction kettle B and the reaction kettle C is higher than 60%.
In the step 4, the light phase separated from the evaporator is sent to a cooler for cooling, and the cooled liquid phase is sent to a rectifying tower for separation; and (3) sending one part of the gas phase cooled by the cooler into a mixer to be mixed with raw materials of methanol, ethylene and CO, and sending the mixed gas phase into a reaction kettle A to participate in ethylene carbonylation reaction, and sending the other part of the gas phase to be recycled.
The multi-kettle serial reaction system consists of a main reactor (reaction kettle A) and an auxiliary reactor (reaction kettle B and/or reaction kettle C), wherein the main reactor has higher methanol content and lower methyl propionate content, the reaction rate is high, and the ethylene carbonylation reaction mainly occurs in the main reactor; the product liquid of the main reactor is input into an auxiliary reactor for further reaction, and the main function of the auxiliary reactor is to improve the methyl propionate content in the reaction liquid so as to be beneficial to product separation. In addition, after the methanol and CO in the reaction liquid are further consumed in the auxiliary reactor, the reaction liquid is sent to a separation refining unit such as evaporation, rectification and the like, and the stability of the catalyst system is improved. The reaction and separation processes are more efficient, the methyl propionate synthesis and separation and purification cost can be effectively reduced, the technical competitiveness is enhanced, and the application prospect is good.
The invention discloses a carbonylation reaction process based on multi-kettle serial connection, which comprises the following steps:
(1) Methanol, ethylene and CO raw materials and materials returned by the separation and refining unit are conveyed to enter a reaction kettle A, and ethylene carbonylation reaction is carried out in the reaction kettle A to synthesize methyl propionate;
(2) The product stream of the reaction kettle A is conveyed to an auxiliary reactor (reaction kettle B), methanol, CO and ethylene are further converted in the auxiliary reactor, the content of methyl propionate in the product liquid is increased, and the content of methanol and dissolved gas is reduced;
(3) Sending the product liquid obtained in the step (2) into an evaporator for separation to obtain a light phase mainly comprising methanol and methyl propionate; the obtained heavy phase mainly comprises methyl propionate, methanol and a catalyst;
(4) Returning the heavy phase obtained in the step (3) to the reaction kettle A, and sending the light phase obtained in the step (3) to a rectifying tower for separation, and recovering the methanol enriched at the top of the rectifying tower to return to the reaction kettle A; and (5) extracting methyl propionate products from the tower bottom of the rectifying tower.
The liquid phase and the gas phase material flow output by the reaction kettle A are respectively or jointly sent into an auxiliary reactor, and the auxiliary reactor consists of one or at least two independent reaction spaces (for example, a reaction kettle B and a reaction kettle C).
The auxiliary reactor consists of two independent reaction spaces, namely a reaction kettle B and a reaction kettle C, and has the main functions of further improving the conversion rate of methanol so as to realize the purpose of increasing the content of methyl propionate in the product liquid and further consuming trace CO dissolved in the product liquid so as to improve the stability of the catalyst.
The auxiliary reactor consists of two independent reaction spaces, namely a reaction kettle B and a reaction kettle C, wherein the liquid phase and the gas phase material flow output by the reaction kettle A are respectively or jointly sent into the reaction kettle B, and in the reaction kettle B, the gas phase ethylene and CO are continuously dissolved into the reaction liquid, the methanol in the reaction liquid is further converted, and the content of the methyl propionate is increased; and the liquid phase material flow output by the reaction kettle B is sent to the reaction kettle C, and trace CO carried by the liquid phase material flow and dissolved in the reaction kettle C is further converted, so that the stability of the catalyst is improved.
The mass content of methanol in the product liquid of the reaction kettle A is higher than 20%, preferably 25% -45%.
The mass content of methyl propionate in the product liquid of the reaction kettle B and the reaction kettle C is higher than 60%, preferably 65% -85%.
And (3) carrying out carbonylation reaction on ethylene, carbon monoxide and methanol to synthesize methyl propionate, wherein the carbonylation reaction temperature is 60-150 ℃, the pressure is 5-30 bar, and the catalyst system is composed of palladium salt, phosphine ligand and cocatalyst.
The heavy phase containing the catalyst output by the evaporator is partially returned to the reaction kettle A and partially sent out, so that the accumulation of high-boiling impurities in a reaction system is reduced, and the catalyst is recovered or/and replenished; and part of the gas returned by the separation and refining unit is returned to the reaction kettle A, and the other part of the gas is discharged, so that the accumulation of impurities such as low-boiling byproducts, inert gases and the like in the reaction system is reduced.
The mixer is arranged in front of the reaction kettle A, and the raw materials of methanol, ethylene and CO and the materials returned by the separation and refining unit are conveyed to the mixer and conveyed into the reaction kettle A by the mixer.
The heavy phase containing the catalyst output by the evaporator returns to the reaction kettle A without passing through a mixer; the raw materials of methanol, ethylene and CO and other materials returned by the separation and refining unit are conveyed to a mixer, an antioxidant is added into the mixer, and after trace oxygen is removed, the raw materials are conveyed from the mixer into a reaction kettle A. The key component phosphine ligand in the olefin carbonylation catalyst system is extremely sensitive to a small amount or a trace amount of oxygen introduced in the processes of reaction liquid, raw material gas (CO, ethylene), material metering transfer and the like, so that the catalyst system is easy to oxidize and deactivate, the problems of catalyst performance reduction, raw material pretreatment, transfer cost increase and the like are caused, and the oxidation of the catalyst system can be effectively inhibited by adding a trace amount of antioxidant and contacting the process material after deoxidization pretreatment of the process material, so that the performance of the catalyst system for preparing methyl propionate by ethylene carbonylation is improved. The principle is as follows: in a small or trace oxygen environment system, the antioxidant preferentially reacts with oxygen, thereby protecting phosphine ligands and palladium-phosphine ligands.
From the standpoint of product separation, the higher the methyl propionate content in the product liquid is, the more advantageous, but an increase in the methyl propionate content will result in a decrease in the reaction rate, which is disadvantageous. In addition, it was found that methanol and dissolved trace CO in the product liquid can induce reduction of divalent palladium to zero-valent, resulting in precipitation of palladium metal and reduced catalyst activity.
The invention provides a carbonylation reaction process based on multi-kettle serial connection, which is provided with a multi-kettle serial reaction system consisting of a reaction kettle A and an auxiliary reactor (reaction kettle B and/or reaction kettle C), wherein the reaction kettle A has higher methanol content and lower methyl propionate content, the reaction rate is high, and the ethylene carbonylation reaction mainly occurs in the reaction kettle A; the product liquid of the reaction kettle A is input into an auxiliary reactor for further reaction, and the main function of the auxiliary reactor is to improve the methyl propionate content in the reaction liquid so as to facilitate product separation; in addition, after the methanol and CO in the reaction liquid are further consumed in the auxiliary reactor, the reaction liquid is sent to a separation refining unit such as evaporation, rectification and the like, and the stability of the catalyst system is improved. The reaction and separation processes are more efficient, the methyl propionate synthesis and separation and purification cost can be effectively reduced, the technical competitiveness is strong, and the application prospect is good. The method can effectively solve the technical problems that the demand of methyl propionate synthesis reaction and methyl propionate separation and purification from reaction liquid on the components of the reaction liquid is left and the palladium metal precipitation and the activity reduction of the catalyst are caused by reduction of divalent palladium in the process of preparing methyl propionate by ethylene carbonylation.
The technology of the present invention is further illustrated by the following examples.
Example 1
Carbonylation reaction evaluation method: weighing a certain amount of palladium salt, phosphine ligand, auxiliary agent and methanol, adding into a 500 mL high-pressure reaction kettle, sealing the high-pressure reaction kettle, replacing and starting stirring, heating the reaction kettle to 80-120 ℃, stirring at a rate of 400-1200 r/min, introducing feed gas into the reaction kettle, boosting to 10-30 bar, starting the reaction, continuously supplementing the feed gas to maintain stable reaction pressure, recording the instantaneous consumption of gas (the index can reflect the conditions of kettle liquid composition, reaction rate change and the like), and taking a liquid phase product for chromatographic analysis after a period of reaction.
The specific process is as follows: 200g of degassed methanol was added to a 500 mL reactor followed by Pd 2 （dba） 3 7mg of 1, 2-bis (di-tert-butyl phosphinomethyl) ferrocene 12mg, 150mg of methylsulfonic acid is added, the high-pressure reaction kettle is sealed, the mixture is replaced and stirred, raw material gases of ethylene and CO are introduced, and the reaction kettle is heated to 100 o And C, when the pressure in the reaction kettle is stabilized at 15bar, starting counting, ending the experiment after 180min, wherein the selectivity of methyl propionate based on ethylene is higher than 99%, and the change curve of the consumption rate of raw material gas with the reaction time is shown in figure 2. The 3h cumulative TON was 97217. After the catalyst is separated from the reaction kettle liquid and re-dosed by referring to the experimental process, the change curves of TOF, TON and raw material gas consumption rate along with the reaction time are similar to those of the fresh catalyst, which indicates that the catalyst is not obviously deactivated and performance is not reduced in the evaluation process. In the reaction process of 180min, the partial pressure of ethylene and CO is kept unchanged, TOF is obviously reduced along with the extension of the reaction time, mainly due to the reactionThe methanol in the reaction kettle liquid is continuously consumed, the content is obviously reduced, and the carbonylation reaction rate of ethylene, CO and methanol is obviously reduced.
Therefore, it is necessary to maintain a higher methanol content in the reaction mixture to improve the reaction rate and the synthesis efficiency.
Example 2
In order to further explain the composition of the reaction solution, particularly the influence of the content of main components of methanol and methyl propionate on the energy consumption of product refining separation, the heat load of a rectifying tower corresponding to the product of obtaining 1 ton of 99.5% methyl propionate with different feed compositions is shown in fig. 3, the rectifying tower used in the illustration operates at normal pressure, 20 theoretical plates are used, and the feed plate is the 10 th plate. The separation requirements set under different feed composition conditions are: the mass content of methanol in the fraction extracted from the top of the rectifying tower is 46%, and the mass content of methyl propionate in the material extracted from the bottom of the rectifying tower is 99.5%.
The result shows that under the same separation equipment and separation requirements, the energy consumption of rectification separation is obviously increased along with the increase of the methanol content and the decrease of the methyl propionate content in the feed, so that the methyl propionate product with unit mass is obtained. Therefore, the reduction of methanol content and the increase of methyl propionate content in the carbonylation reaction product liquid are advantageous for reducing separation energy consumption. In addition, the increase of methyl propionate content in the product liquid also means that the material circulation amount is reduced, and is also beneficial to reducing the equipment size, pumping power consumption and the like.
Example 3
As shown in fig. 1, the methanol, ethylene, CO raw materials and the materials returned from the separation and refining unit are conveyed into a mixer, the mixer is connected with a reaction kettle a, and the outlet of the reaction kettle a is connected with a reaction kettle B; a gas-liquid separator is arranged behind the reaction kettle B, a gas-phase material flow outlet is connected to the mixer, and a liquid-phase material flow outlet is connected to the reaction kettle C; the outlet of the reaction kettle C is connected to an evaporator, the heavy phase outlet of the evaporator is connected to a mixer, and the light phase outlet of the evaporator is connected to a cooler; the gas phase material flow outlet of the cooler is connected to the mixer, and the liquid phase material flow outlet is connected to the rectifying tower; the outlet of the stream extracted from the top of the rectifying tower is connected to a mixer, and the methyl propionate product is extracted from the tower bottom.
The operating temperatures of the reaction kettle A, the reaction kettle B and the reaction kettle C are 100 ℃, the operating pressure is 15bar, and the residence time is 15min, 12min and 2min respectively.
The mass contents of methanol and methyl propionate in the materials at the inlet and outlet of the main equipment are respectively as follows:
34% of methanol in the product liquid of the reaction kettle A, 27% of methanol in the product liquid of the reaction kettle B, 26.8% of methanol in the product liquid of the reaction kettle C, 30.5% of methanol in the feed of the rectifying tower, 46% of methanol in the top extract of the rectifying tower and 0.1% of methanol in the bottom extract of the rectifying tower;
methyl propionate in the product liquid of the reaction kettle A is 65%, methyl propionate in the product liquid of the reaction kettle B is 72%, methyl propionate in the product liquid of the reaction kettle C is 72.2%, methyl propionate in the feed of the rectifying tower is 69.5%, methyl propionate in the top extract of the rectifying tower is 54%, and methyl propionate in the bottom extract of the rectifying tower is 99.9%.
Finally, it should be noted that: the above embodiments are merely preferred embodiments of the present invention for illustrating the technical solution of the present invention, but not limiting the scope of the present invention; 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 corresponding technical solutions; that is, even though the main design concept and spirit of the present invention is modified or finished in an insubstantial manner, the technical problem solved by the present invention is still consistent with the present invention, and all the technical problems are included in the protection scope of the present invention; in addition, the technical scheme of the invention is directly or indirectly applied to other related technical fields, and the technical scheme is included in the scope of the invention.
Claims (6)
1. The carbonylation reaction system based on multi-kettle serial connection is characterized by comprising a reaction kettle A (1), a reaction kettle B (2) connected with the reaction kettle A (1), an evaporator (3) connected with the reaction kettle B (2), a rectifying tower (4) connected with the evaporator (3) and a methyl propionate product external conveying pipe (5) connected with the rectifying tower (4) at the tower kettle; the reaction kettle A (1) is connected with a material conveying pipe; a light phase outlet of the evaporator (3) is connected with a cooler (11), a liquid phase material flow outlet of the cooler (11) is connected to the rectifying tower (4), the evaporator (3) is connected to the rectifying tower (4) through the cooler (11), and a gas phase material flow outlet of the cooler (11) is connected to the reaction kettle A (1);
a gas-liquid separator (10) is connected from the reaction kettle B (2), a liquid phase outlet of the gas-liquid separator (10) is connected to the evaporator (3), a gas phase outlet of the gas-liquid separator is connected to the reaction kettle A (1), and the reaction kettle B (2) is connected to the evaporator (3) through the gas-liquid separator (10);
a reaction kettle C (9) is connected from a liquid phase outlet of the gas-liquid separator (10), the reaction kettle C (9) is connected to the evaporator (3), and a liquid phase outlet of the gas-liquid separator (10) is connected to the evaporator (3) through the reaction kettle C (9);
the heavy phase outlet of the evaporator (3) is connected to the reaction kettle A (1), and the top of the rectifying tower (4) is connected to the reaction kettle A (1) through a pipeline;
the material conveying pipe comprises an ethylene conveying pipe (6), a methanol conveying pipe (7) and a carbon monoxide conveying pipe (8).
2. The carbonylation reaction system according to claim 1, further comprising a mixer (12) connected to the reaction vessel a (1), a transfer line connected to the reaction vessel a (1), and equipment other than the evaporator (3) are connected to the mixer (12) and connected to the reaction vessel a (1) through the mixer (12).
3. A reaction process based on a multi-tank series carbonylation reaction system according to claim 1 or 2, comprising the steps of:
step 1, conveying raw materials of methanol, ethylene and CO to a reaction kettle A for ethylene carbonylation reaction to synthesize methyl propionate;
step 2, conveying the product stream after the reaction in the reaction kettle A to the reaction kettle B to continue the ethylene carbonylation reaction;
step 3, conveying the product material flow after the reaction in the reaction kettle B to an evaporator for separation;
and 4, sending the light phase separated from the evaporator into a rectifying tower for separation, and obtaining a methyl propionate product to be extracted from the bottom of the rectifying tower.
4. The reaction method according to claim 3, wherein in the step 1, the temperature at which the carbonylation reaction of methanol, ethylene and CO raw materials occurs is 60-150 ℃ and the pressure is 5-30 bar, and the catalyst system in the reaction kettle a is composed of palladium salt, phosphine ligand and cocatalyst;
in the step 3, a part of the heavy phase separated from the evaporator is sent to a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part is sent to the outside to recover the catalyst therein;
in the step 4, the enriched methanol at the top of the rectifying tower is extracted, one part of the methanol is sent into a mixer to be mixed with raw materials of methanol, ethylene and CO and then is sent into a reaction kettle A to participate in the ethylene carbonylation reaction, and the other part of the methanol is sent and recovered.
5. The reaction method according to claim 3, wherein in the step 3, the product stream after the reaction in the reaction vessel B is separated from the liquid phase by a gas-liquid separator and is sent to the reaction vessel C for further ethylene carbonylation reaction, and the product stream after the reaction in the reaction vessel C is sent to an evaporator for separation;
one part of the gas phase separated by the gas-liquid separator is sent to a mixer to be mixed with raw materials of methanol, ethylene and CO, and then is sent to a reaction kettle A to participate in ethylene carbonylation reaction, and the other part is sent to be recycled;
the mass content of methanol in the product liquid in the reaction kettle A is higher than 20%, and the mass content of methyl propionate in the product liquid in the reaction kettle B and the reaction kettle C is higher than 60%.
6. A reaction method according to claim 3, wherein in said step 4, the light phase separated from the evaporator is first sent to a cooler for cooling, and the cooled liquid phase is sent to a rectifying column for separation;
and (3) sending one part of the gas phase cooled by the cooler into a mixer to be mixed with raw materials of methanol, ethylene and CO, and sending the mixed gas phase into a reaction kettle A to participate in ethylene carbonylation reaction, and sending the other part of the gas phase to be recycled.
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