阅读说明：本技术 一种丁醛的制备方法和制备装置 (Preparation method and preparation device of butyraldehyde ) 是由 杨建春 于 2020-04-02 设计创作，主要内容包括：本发明公开一种丁醛的制备方法和制备装置,将丙烯和合成气在羰基化反应器中进行羰基化反应,从羰基化反应器中采出两股反应产物物料；其中,一股反应产物物料经过分离,得到丁醛混合物；另一股反应产物物料、记为体外循环反应液,与换热介质进行换热后,得到温度降低的反应液和气相换热介质；所述温度降低的反应液返回所述羰基化反应器,所述气相换热介质经增压后送入丁醛精馏塔,与塔底物料和/或进料换热,得到液态换热介质,所述液态换热介质返回与体外循环反应液换热。通过换热介质循环将羰基化反应热用作丁醛分离塔的热源,降低丙烯羰基化反应装置的能源消耗,节约了操作成本。(The invention discloses a preparation method and a preparation device of butyraldehyde, which carry out carbonylation reaction on propylene and synthesis gas in a carbonylation reactor, and extract two reaction product materials from the carbonylation reactor; wherein, a reaction product material is separated to obtain a butyraldehyde mixture; the other strand of reaction product material is marked as an extracorporeal circulation reaction liquid, and after heat exchange is carried out on the extracorporeal circulation reaction liquid and a heat exchange medium, the reaction liquid with reduced temperature and a gas phase heat exchange medium are obtained; the reaction liquid with the reduced temperature returns to the carbonylation reactor, the gas phase heat exchange medium is pressurized and then sent to a butyraldehyde rectifying tower to exchange heat with the materials and/or the feeding materials at the bottom of the tower to obtain a liquid heat exchange medium, and the liquid heat exchange medium returns to exchange heat with the extracorporeal circulation reaction liquid. The carbonylation reaction heat is used as the heat source of the butyraldehyde separation tower through the circulation of the heat exchange medium, so that the energy consumption of the propylene carbonylation reaction device is reduced, and the operation cost is saved.)

1. A process for the preparation of butyraldehyde, comprising: carrying out carbonylation reaction on propylene and synthesis gas in a carbonylation reactor, and extracting two reaction product materials from the carbonylation reactor; wherein, a reaction product material is separated to obtain a butyraldehyde mixture; the other strand of reaction product material is marked as an extracorporeal circulation reaction liquid, and after heat exchange is carried out on the extracorporeal circulation reaction liquid and a heat exchange medium, the reaction liquid with reduced temperature and a gas phase heat exchange medium are obtained; the reaction liquid with the reduced temperature returns to the carbonylation reactor, the gas-phase heat exchange medium exchanges heat with the material and/or the feeding material at the bottom of the butyraldehyde rectifying tower after being pressurized to obtain a liquid heat exchange medium, and the liquid heat exchange medium returns to exchange heat with the extracorporeal circulation reaction liquid.

2. The process of claim 1, wherein said separating is carried out to separate butyraldehyde mixture in said reaction product stream from unreacted propylene, synthesis gas components, and catalyst used in the carbonylation reaction.

3. The production method according to claim 1 or 2, wherein the heat exchange medium is at least one selected from the group consisting of hydrocarbons having a boiling point of less than 120 ℃, alcohols, ketones, amines, esters, water, carbon dioxide and ammonia gas.

4. The preparation method according to any one of claims 1 to 3, wherein the butyraldehyde mixture enters the butyraldehyde rectifying tower to be rectified to obtain separated isobutyraldehyde, n-butyraldehyde and n-butyraldehyde containing high-boiling components;

preferably, the butyraldehyde rectification column is used for separating the butyraldehyde mixture;

preferably, the butyraldehyde mixture contains at least n-butyraldehyde and isobutyraldehyde, optionally with high boilers.

5. The production method according to any one of claims 1 to 4, wherein the butyraldehyde rectifying column is provided with an overhead condenser, and a part of the material is refluxed to the top of the column and a part of the material is extracted through the overhead condenser;

preferably, n-butyraldehyde is extracted from a side line of the butyraldehyde rectifying tower, and n-butyraldehyde containing high-boiling-point substances is extracted from the bottom of the butyraldehyde rectifying tower;

preferably, a tower bottom reboiler is arranged at the tower bottom of the butyraldehyde rectifying tower, the pressurized gas-phase heat exchange medium is fed into the tower bottom reboiler to exchange heat with tower bottom liquid entering the tower bottom reboiler, and the obtained tower bottom liquid with the raised temperature returns to the butyraldehyde rectifying tower;

preferably, the tower bottom liquid of the butyraldehyde rectifying tower can also be directly extracted;

preferably, the butyraldehyde rectifying tower is provided with a feeding heater, and the pressurized gas-phase heat exchange medium is fed into the feeding heater to exchange heat with the feeding in the feeding heater.

6. A butyraldehyde production apparatus, characterized in that the apparatus comprises: the device comprises a carbonylation reactor, a heat exchanger, a compressor, a butyraldehyde rectifying tower, a tower kettle reboiler and/or a feeding heater;

the heat exchanger comprises a material inlet, a material outlet, a heat exchange medium inlet and a heat exchange medium outlet;

an extracorporeal circulation reaction liquid outlet of the carbonylation reactor is connected with a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected with the bottom of the carbonylation reactor; and the heat exchange medium outlet of the heat exchanger is connected with the tower kettle reboiler and/or the feeding heater through the compressor, and the heat exchange medium outlet of the tower kettle reboiler and/or the feeding heater is connected with the heat exchange medium inlet of the heat exchanger.

7. The preparation device according to claim 6, wherein the kettle reboiler is arranged at the bottom of the butyraldehyde rectifying tower;

preferably, a tower bottom liquid inlet of the tower bottom reboiler is connected with the tower bottom of the butyraldehyde rectifying tower, a tower bottom liquid outlet of the tower bottom reboiler is connected with the tower bottom of the butyraldehyde rectifying tower, and the tower bottom liquid after temperature rise returns to the butyraldehyde rectifying tower.

8. The preparation device of claim 6 or 7, wherein the butyraldehyde rectification column is provided with a material inlet pipeline, a feed heater is arranged on the material inlet pipeline, and a feed outlet of the feed heater is connected with a material inlet of the butyraldehyde rectification column.

9. The preparation device according to any one of claims 6 to 8, characterized by further comprising a condenser, wherein the top of the butyraldehyde rectifying tower is connected with a material inlet of the condenser, a material outlet of the condenser is connected with two branches, one branch is connected with the top of the butyraldehyde rectifying tower, and the other branch is an overhead condensate extraction pipeline;

preferably, the butyraldehyde rectifying tower further comprises a side line extraction pipeline, and the side line extraction pipeline is used for extracting n-butyraldehyde;

preferably, the carbonylation reactor further comprises a reaction product material withdrawal line for withdrawal of a portion of the reaction product material.

10. Use of a process according to any one of claims 1 to 5 and/or an apparatus according to any one of claims 6 to 9 in the preparation of butyraldehyde.

Technical Field

The invention belongs to the field of butyraldehyde preparation, and particularly relates to a preparation method and a preparation device of butyraldehyde.

Background

With the rapid development of petrochemical industry, coal chemical industry and organic chemical industry, the butanol-octanol industry expands rapidly. The core process of butanol-octanol production is to use propylene, synthesis gas and hydrogen as raw materials and rhodium-phosphine complex as a catalyst to carry out oxo-synthesis of n-butyraldehyde, wherein the oxo-synthesis reaction process is accompanied by generation of isobutyraldehyde, so that the main product of the oxo-synthesis is mixed aldehyde of the n-butyraldehyde and the isobutyraldehyde; after rectification and separation, n-butyraldehyde enters a downstream condensation-hydrogenation process to produce octanol (isooctanol), isobutyraldehyde produced at the tower top or a mixture of n-butyraldehyde and isobutyraldehyde (n/iso is 3.5:1) is subjected to a hydrogenation process to produce mixed alcohol, and n-butanol and a byproduct isobutanol are further separated. In recent years, the markets of n-octyl alcohol and n-butyl alcohol are basically saturated in China, but the market gap of isobutyraldehyde is large, so that the technical improvement of the existing butanol and octanol production device is promoted, the output proportion of isobutyraldehyde is increased, and the separation of isobutyraldehyde and n-butyl aldehyde is enhanced.

In the process of preparing butyraldehyde by propylene carbonylation, the carbonylation reaction and the rectification separation of butyraldehyde mixture are concentrated areas of energy consumption. The enthalpy of the propylene carbonylation reaction is-126.6 kJ/mol, the reaction process is accompanied by a large amount of reaction heat emission, and part of reaction liquid is generally circulated externally in industry, exchanges heat with circulating water and removes the reaction heat; while the reaction product separation unit, especially the rectification column, requires a heat source usually supplied by steam. The process has the defect of high energy consumption of circulating water, steam and the like, and is not beneficial to market competition. How to reduce the energy consumption in the butyraldehyde preparation process becomes an important technical improvement direction.

Disclosure of Invention

The invention provides a preparation method of butyraldehyde, which comprises the following steps:

carrying out carbonylation reaction on propylene and synthesis gas in a carbonylation reactor, and extracting two reaction product materials from the carbonylation reactor; wherein, a reaction product material is separated to obtain a butyraldehyde mixture; the other strand of reaction product material is marked as an extracorporeal circulation reaction liquid, and after heat exchange is carried out on the extracorporeal circulation reaction liquid and a heat exchange medium, the reaction liquid with reduced temperature and a gas phase heat exchange medium are obtained; the reaction liquid with the reduced temperature returns to the carbonylation reactor, the gas phase heat exchange medium is pressurized and then sent to a butyraldehyde rectifying tower to exchange heat with the materials and/or the feeding materials at the bottom of the tower to obtain a liquid heat exchange medium, and the liquid heat exchange medium returns to exchange heat with the extracorporeal circulation reaction liquid.

According to an embodiment of the present invention, the carbonylation reaction is part of a propylene carbonylation synthesis unit in a butyraldehyde production process. Wherein, the propylene and the synthesis gas react in a carbonylation reactor under the action of a catalyst to generate a reaction product material. The amounts and proportions of propylene and synthesis gas, and the amount and choice of catalyst are not particularly limited and can be selected by those skilled in the art under conditions known in the art.

According to an embodiment of the invention, the separating is to separate a butyraldehyde mixture in the reaction product stream from unreacted propylene, syngas, and catalyst. For example, the separation may be performed in an evaporator.

According to an embodiment of the invention, the heat exchange medium is selected from at least one of hydrocarbons with boiling points below 120 ℃, alcohols, ketones, amines, esters, water, carbon dioxide and ammonia, for example the hydrocarbon may be selected from at least one of butane, isobutane, pentane, cyclopentane, etc.; the ketone may be acetone; illustratively, the heat exchange medium is cyclopentane.

According to the embodiment of the invention, the butyraldehyde mixture enters the butyraldehyde rectifying tower to be rectified to obtain the separated isobutyraldehyde, n-butyraldehyde and high-boiling-point substance-containing n-butyraldehyde.

According to an embodiment of the present invention, the high boiling substance means a substance having a boiling point higher than that of n-butyraldehyde in the reaction product.

According to an embodiment of the invention, the butyraldehyde mixture may also be passed through a stripping column and a stabilizer column prior to entering the butyraldehyde rectification column.

According to an embodiment of the invention, the butyraldehyde rectification column is used to separate the butyraldehyde mixture. Wherein the butyraldehyde mixture contains at least n-butyraldehyde and isobutyraldehyde, and optionally contains a high boiling substance. For example, the high boiling substance is a C12-20 high boiling substance. As another example, the butyraldehyde mixture contains 5 to 15 wt% of isobutyraldehyde, 85 to 94 wt% of n-butyraldehyde, and 0.5 to 1.5 wt% of C12 high boiling substance, and illustratively contains 9.5 wt% of isobutyraldehyde, 89.5 wt% of n-butyraldehyde, and 1.0 wt% of C12 high boiling substance.

According to the embodiment of the invention, the butyraldehyde rectifying tower is provided with a tower top condenser, isobutyraldehyde or a mixture of isobutyraldehyde and n-butyraldehyde extracted from the tower top passes through the tower top condenser, a part of materials flows back to the tower top, and a part of materials are extracted.

According to the embodiment of the invention, the n-butyraldehyde is extracted from the side line of the butyraldehyde rectifying tower, and the n-butyraldehyde containing high-boiling components is extracted from the bottom of the butyraldehyde rectifying tower.

According to the embodiment of the invention, a tower bottom reboiler is arranged at the tower bottom of the butyraldehyde rectifying tower, the pressurized gas-phase heat exchange medium can be fed into the tower bottom reboiler to exchange heat with tower bottom liquid entering the tower bottom reboiler, and the obtained tower bottom liquid with the raised temperature returns to the butyraldehyde rectifying tower.

According to the embodiment of the invention, the tower bottom liquid of the butyraldehyde rectifying tower can also be directly extracted.

According to the embodiment of the invention, the butyraldehyde rectifying tower is provided with a feeding heater, and the pressurized gas-phase heat exchange medium can be fed into the feeding heater to exchange heat with the feeding in the feeding heater.

According to an embodiment of the invention, the heat exchange may be performed in a heat exchanger.

The invention also provides a butyraldehyde preparation device, which comprises: the device comprises a carbonylation reactor, a heat exchanger, a compressor, a butyraldehyde rectifying tower, a tower kettle reboiler and/or a feeding heater;

the heat exchanger comprises a material inlet, a material outlet, a heat exchange medium inlet and a heat exchange medium outlet;

an extracorporeal circulation reaction liquid outlet of the carbonylation reactor is connected with a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected with the bottom of the carbonylation reactor; and the heat exchange medium outlet of the heat exchanger is connected with the tower kettle reboiler and/or the feeding heater through the compressor, and the heat exchange medium outlet of the tower kettle reboiler and/or the feeding heater is connected with the heat exchange medium inlet of the heat exchanger.

According to an embodiment of the invention, the kettle reboiler is arranged at the bottom of the butyraldehyde rectifying tower. And a tower bottom liquid inlet of the tower bottom reboiler is connected with the tower bottom of the butyraldehyde rectifying tower, a tower bottom liquid outlet of the tower bottom reboiler is connected with the tower bottom of the butyraldehyde rectifying tower, and the tower bottom liquid after temperature rise returns to the butyraldehyde rectifying tower.

According to the embodiment of the invention, the butyraldehyde rectifying tower is provided with a material inlet pipeline, and a feeding heater is arranged on the material inlet pipeline, wherein a feeding outlet of the feeding heater is connected with a material inlet of the butyraldehyde rectifying tower.

According to the embodiment of the invention, the device further comprises a condenser, the top of the butyraldehyde rectifying tower is connected with a material inlet of the condenser, a material outlet of the condenser is connected with two branches, one branch is connected with the top of the butyraldehyde rectifying tower, and the other branch is a top condensate extraction pipeline.

According to an embodiment of the invention, the butyraldehyde distillation column further comprises a side draw line for drawing n-butyraldehyde.

According to an embodiment of the invention, the carbonylation reactor further comprises a reaction product material withdrawal line for withdrawal of a portion of the reaction product material.

In the present invention, the term "connection" refers to a connection known in the art, such as a pipeline connection.

According to an exemplary embodiment of the present invention, the apparatus for preparing butyraldehyde comprises: the device comprises a carbonylation reactor, a heat exchanger, a compressor, a butyraldehyde rectifying tower and a tower kettle reboiler;

the tower kettle reboiler is connected with a tower kettle of the butyraldehyde rectifying tower;

the heat exchanger comprises a material inlet, a material outlet, a heat exchange medium inlet and a heat exchange medium outlet;

an extracorporeal circulation reaction liquid outlet of the carbonylation reactor is connected with a material inlet of the heat exchanger, and a material outlet of the heat exchanger is connected with the bottom of the carbonylation reactor; and a heat exchange medium outlet of the heat exchanger is connected with the tower kettle reboiler through the compressor, and a heat exchange medium outlet of the tower kettle reboiler is connected with a heat exchange medium inlet of the heat exchanger.

The invention also provides the application of the device and/or the method in the separation of butyraldehyde (n-butyraldehyde/isobutyraldehyde).

The invention has the beneficial effects that:

according to the butyraldehyde preparation method and the butyraldehyde preparation device, a part of reaction product materials extracted from a carbonylation reactor exchange heat with a heat exchange medium to obtain a gas-phase heat exchange medium and reaction product materials with reduced temperature, the reaction product materials with reduced temperature are returned to a carbonylation reaction system, the gas-phase heat exchange medium is pressurized, the pressurized heat exchange medium is sent to a reboiler at the bottom of a butyraldehyde rectification tower and/or a feeding heater to be used as a heat source of tower bottom liquid and/or feeding, and the liquid-phase heat exchange medium obtained after heat exchange is returned to be used for exchanging heat with the part of reaction product materials extracted from the carbonylation reactor; isobutyraldehyde is collected from the top of the butyraldehyde rectifying tower, and n-butyraldehyde is collected from the side line and/or the bottom of the butyraldehyde rectifying tower. The invention uses the carbonylation reaction heat as the heat source of the butyraldehyde rectifying tower through the circulation of the heat exchange medium, reduces the energy consumption of the propylene carbonylation reaction device and saves the operation cost.

Drawings

Fig. 1 is a schematic structural diagram of a butyraldehyde preparation apparatus provided in example 1.

Reference numerals: A. the device comprises a carbonylation reactor, a heat exchanger B, a compressor C, a butyraldehyde rectifying tower D, a tower kettle reboiler E, a tower kettle reboiler F and a condenser; 1. the method comprises the following steps of (1) feeding a pipeline, (2) partial reaction products, (3) an extracorporeal circulation reaction liquid, (4) heat exchange cooling reaction materials, (5) a vaporized heat exchange medium, (6) pressurized heat exchange medium gas, (7) heat exchange medium condensate, (10) a butyraldehyde mixture, (11) tower top gas phase materials, (12) tower top reflux materials, (13) tower top extraction materials, (14) side line extraction materials, (15) tower bottom liquid, (16) tower bottom liquid with increased temperature, (17) tower bottom extraction materials.

Detailed Description

In the preparation method of butyraldehyde provided by the foregoing, propylene and synthesis gas are subjected to carbonylation reaction in a reactor, and two reaction product materials are withdrawn from the carbonylation reactor; wherein, a reaction product material is separated to obtain a butyraldehyde mixture; the other strand of reaction product material is marked as an extracorporeal circulation reaction liquid, and after heat exchange is carried out on the extracorporeal circulation reaction liquid and a heat exchange medium, the reaction liquid with reduced temperature and a gas phase heat exchange medium are obtained; the reaction liquid with the reduced temperature returns to the carbonylation reactor, the gas phase heat exchange medium is pressurized and then sent to a butyraldehyde rectifying tower to exchange heat with the materials and/or the feeding materials at the bottom of the tower to obtain a liquid heat exchange medium, and the liquid heat exchange medium returns to exchange heat with the extracorporeal circulation reaction liquid.

According to an embodiment of the present invention, the carbonylation reaction is part of a propylene carbonylation synthesis unit in a butyraldehyde production process. Wherein, the propylene and the synthesis gas react in a carbonylation reactor under the action of a catalyst to generate a reaction product material. The amounts and proportions of propylene and synthesis gas, the amount and choice of catalyst, and the operating conditions for the carbonylation reaction are not particularly limited and can be selected by those skilled in the art as is known in the art. For example, the syngas includes carbon monoxide, hydrogen, and methane.

For example, the feed mass ratio of syngas to propylene is 1 (1.01-2), such as 1 (1.2-1.6), exemplary 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.57, 1:1.6, 1: 1.7.

For example, the catalyst may be selected from rhodium phosphine complexes.

For example, the feed temperature for the carbonylation reaction may be room temperature, such as 20 ℃ to 30 ℃, illustratively 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃.

For example, the feed pressure for the carbonylation reaction is from 2.2 to 3.0MPa, such as from 2.3 to 2.5MPa, illustratively 2.3MPa, 2.5 MPa.

For example, the carbonylation reaction temperature is 90-101 ℃, such as 90 ℃, 93 ℃, 95 ℃, 97 ℃, 100 ℃, 101 ℃.

For example, the temperature of the extracorporeal circulation reaction solution is substantially the same as the temperature of the carbonylation reaction.

According to an embodiment of the invention, the production mass ratio of the extracorporeal circulation reaction solution to the reaction product mass is (5-20):1, for example (8-15):1, exemplary 5:1, 7:1, 8:1, 10:1, 11:1, 12:1, 15:1, 17:1, 20: 1.

According to an embodiment of the invention, the butyraldehyde mixture is fed in an amount of 15000-30000kg/h, such as 18000-25000kg/h, illustratively 15000kg/h, 18000kg/h, 20000kg/h, 22000kg/h, 25000 kg/h.

According to an embodiment of the invention, the butyraldehyde mixture is fed at a temperature of from 40 to 60 deg.C, such as from 45 to 55 deg.C, illustratively 45 deg.C, 48 deg.C, 50 deg.C, 53 deg.C, 55 deg.C, 58 deg.C, 60 deg.C.

According to an embodiment of the invention, the feed pressure of the butyraldehyde mixture is in the range of from 0.05 to 0.2MPa, for example from 0.1 to 0.16MPa, illustratively 0.08MPa, 0.1MPa, 0.12MPa, 0.13MPa, 0.15 MPa.

According to an embodiment of the invention, the operating temperature of the top of the butyraldehyde rectification column is in the range of from 65 to 80 ℃, such as from 70 to 75 ℃, illustratively 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃.

According to an embodiment of the invention, the operating pressure at the top of the butyraldehyde rectification column is in the range of from 0.05 to 0.2MPa, for example from 0.1 to 0.16MPa, exemplary 0.08MPa, 0.1MPa, 0.12MPa, 0.13MPa, 0.15 MPa.

According to an embodiment of the invention, the operating temperature of the bottom of the butyraldehyde rectification column is 80-100 ℃, for example 85-95 ℃, exemplary 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃.

According to an embodiment of the invention, the operating pressure of the bottom of the butyraldehyde rectification column is 0.05 to 0.2MPa, such as 0.1 to 0.16MPa, illustratively 0.08MPa, 0.1MPa, 0.12MPa, 0.13MPa, 0.15 MPa.

According to an embodiment of the invention, the reflux ratio of the butyraldehyde rectification column is in the range of from 10 to 60, such as from 20 to 50, illustratively 20, 30, 33, 40, 50.

According to an embodiment of the invention, the pressure of the pressurized gas phase heat exchange medium is 0.3-0.5MPa, such as 0.3-0.45MPa, exemplary 0.3MPa, 0.33MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5 MPa.

According to an embodiment of the present invention, the temperature of the pressurized gas phase heat exchange medium is higher than the temperature of the bottom liquid of the column, for example, the temperature of the pressurized gas phase heat exchange medium is 95-110 ℃, such as 100-.

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.