CN112663078A - Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile - Google Patents
Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile Download PDFInfo
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 238000000066 reactive distillation Methods 0.000 claims abstract description 18
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of adiponitrile preparation, and particularly relates to a device and a method for preparing adiponitrile by integrating acrylonitrile electrolytic reaction into a reaction rectifying tower. The reactive distillation column consists of a distillation section, a reaction section and a stripping section, condensers are arranged at the top of the column, the reaction section and the distillation section, a reboiler is arranged at the bottom of the column, and a positive and negative electrode array is arranged at the reaction section; after acrylonitrile, supporting electrolyte, water and other auxiliary components are introduced into a reactive distillation tower, high-selectivity adiponitrile is generated at a cathode acrylonitrile, and oxygen is generated at an anode water by oxidation; finally, oxygen is discharged from the top of the tower, and heavy components of adiponitrile, water, salt and a small amount of by-products are extracted from the bottom of the tower. The invention integrates the electrolytic dimerization reaction of acrylonitrile into the reaction rectifying tower, solves the problems of low single-pass conversion rate and poor selectivity of acrylonitrile, volume expansion of reactant stream caused by anodic oxygen evolution and the like in a common parallel plate type electrolytic cell, and has the conversion rate of acrylonitrile as high as 99 percent and the selectivity of the obtained adiponitrile more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of adiponitrile preparation, and particularly relates to a method for preparing adiponitrile by integrating an electrolysis device into a reaction rectifying tower.
Background
Adiponitrile (ADN), also known as 1, 4-dicyanobutane, is an important chemical raw material, is mainly used for preparing intermediate hexamethylene diamine of polyamide nylon 6, can also be used for preparing rubber additives, insecticides, bactericides and high polymer materials, can also be used as plasticizers, textile additives, solvents, extracting agents and the like, and has wide application.
Currently, Adiponitrile (ADN) is produced industrially mainly by thermochemical catalytic cyanation of 1, 3-butadiene or electrochemical dimerization of Acrylonitrile (AN), wherein the electrochemical dimerization process is less toxic, more environmentally friendly and requires only one reaction step than the conventional butadiene process, and thus is more sustainable and competitive in the future.
The process for the electrolytic dimerization of Acrylonitrile (AN) was first developed successfully in the 60 s of the 20 th century by the company montmorindo usa, with great practical significance, and many methods for carrying out this reaction have been developed today, for example electrolysis in electrolytic cells separated by diaphragms or in undivided electrolytic cells. Among them, the patents US3193475, US3193481, US3616319, US3335162 disclose a process for the electrolytic dimerization of AN in diaphragm-divided electrolytic cells, which is attractive enough to be used industrially for a long time, but requires high energy consumption for the electrolysis, the cell structure is generally complicated and the diaphragms need to be replaced regularly. Compared with the electrolytic cell separated by the diaphragm, the undivided electrolytic cell has simple design, low cell voltage and easy industrial operation, and is a direct electrosynthesis process. For example, US3898140, US3689382 disclose a process for the preparation of adiponitrile by electrolysis of AN aqueous AN solution in a diaphragm-free electrolytic cell, and later US4789442, further improves the efficiency of the reaction by electrolysis of AN emulsion consisting of AN aqueous phase and AN organic phase on a lead or lead alloy cathode. German Basff company also adopts a special capillary gap electrolytic cell (patent US3616320) to establish a diaphragm-free electrolytic device, reduces the ohmic pressure drop and energy consumption of solution by reducing the electrode gap to form a capillary gap reactor of a film electrolyte, but as with other electrolytic processes, electrochemical reduction or oxidation reaction can only respectively occur on the wall of a parallel plate type cathode or anode, the electrode area corresponding to the unit volume of reaction liquid is very small, so the conversion rate of AN per pass is not high, and the AN of outlet liquid needs to be recycled to the electrolytic cell through a large amount of separation operation, thereby increasing the operation difficulty and the cost. If the conversion is increased simply by increasing the current density or the electrode area, the by-products increase due to the decrease of the AN concentration at the latter stage of the reaction, and the process performance is rather lowered. In addition, half a mole of oxygen is generated at the anode while 1 mole of ADN is generated at the cathode, and when the conversion rate is high, the reaction flow volume between the electrode plates greatly expands, which not only reduces the local residence time, but also hinders the contact between the electrolyte solution and the electrode, and makes the operation difficult.
In order to overcome the defects of the traditional electrolytic bath in the ADN electrolytic synthesis process, further improve the conversion rate of AN, reduce the separation procedure and the generation of byproducts, and continuously remove gaseous oxygen in the emulsion, a new process for preparing ADN by electrolyzing AN is required to be found.
Disclosure of Invention
The invention aims to provide a device and a method for preparing Adiponitrile (ADN) by integrating electrolytic reaction into a reaction rectifying tower, overcomes the defects in the conventional Acrylonitrile (AN) electrolytic dimerization process, provides a process for preparing adiponitrile by integrating electrolytic reaction and phase separation, reduces the cost, improves the Acrylonitrile (AN) conversion rate and obtains AN Adiponitrile (ADN) product with high selectivity.
An apparatus and method for the preparation of adiponitrile by the electrolytic dimerization of acrylonitrile comprising: the reactive rectification tower R001 consists of a rectification section, a reaction section and a stripping section, a condenser D001 is arranged at the top of the tower, a reboiler E001 is arranged at the bottom of the tower, and a plurality of positive and negative electrodes are arranged at the reaction section; introducing one or more material flows containing acrylonitrile, supporting electrolyte, water and other auxiliary components into a reactive distillation column R001, generating adiponitrile at a cathode acrylonitrile high selectivity, and simultaneously oxidizing anode water to generate oxygen; and finally, discharging oxygen through a condenser D001 at the top of the tower, and extracting heavy components adiponitrile, water, salt and a small amount of by-products from a reboiler E001 at the bottom of the tower.
The reaction section and the rectifying section of the reaction rectifying tower are provided with a plurality of intermediate condensers C001-C005.
The mass fraction of acrylonitrile, the mass fraction of supporting electrolyte and the mass fraction of water in the feed stream are respectively 1-90%, 1-20% and 10-95%.
The pressure of the R001 of the reactive distillation tower is 0.5-10 atm, the temperature of the top of the tower is-20 ℃, the temperature of the bottom of the tower is 90-250 ℃, and the reboiling ratio of the bottom of the tower is 0.5-3.
The reaction rectifying tower R001 is provided with 30-100 theoretical plates, wherein the rectifying section is provided with 5-50 theoretical plates, and the feeding plate is positioned at the 10 th-21 th theoretical plate.
The total surface area of the cathode corresponding to the unit acrylonitrile feeding flow (1kg/h) in the reaction rectifying tower R001 is 200-1000 m2The current density is 10 to 10000A/m2。
The cathode is a mesh material formed by one or more of lead, cadmium and alloy thereof, and the anode material is stainless steel, Ti \ RuO2、Ti\IrO2Etc. to form a web material.
The cathode and anode are installed in the liquid phase flow region of reactive distillation column R001.
The tower top condenser D001 is a partial condenser, and the purity of the oxygen at the tower top is 90-100%.
The supporting electrolyte is one or more of phosphate and hydrogen phosphate, preferably dipotassium hydrogen phosphate and sodium phosphate.
Advantageous effects
The invention has the advantages that
By integrating the acrylonitrile electrolytic dimerization reaction into the reaction rectifying tower, the gaseous oxygen in the emulsion can be removed while the reaction is carried out, and the problems of low acrylonitrile single-pass conversion rate, reactor volume expansion caused by the anode oxygen evolution reaction and the like in a common parallel plate type electrolytic cell are solved. Compared with the traditional acrylonitrile electrolytic dimerization process, the acrylonitrile conversion rate is improved to 99%, the selectivity of the obtained adiponitrile product is more than 95%, and the separation operation difficulty and the cost are reduced. The reaction rectifying tower is introduced with a plurality of intermediate condensers, so that the load of the condenser at the top of the tower is reduced, the cost is saved, and the change of the gas-liquid flow in a reaction area can be kept in a narrow range, thereby being beneficial to the design and operation of the rectifying tower and the uniform occurrence of electrolytic reaction.
Drawings
FIG. 1 is a schematic view of a reaction apparatus for preparing adiponitrile by electrolytic dimerization of acrylonitrile according to the present invention.
Detailed Description
The invention aims to provide a novel device and a novel method for preparing adiponitrile by electrolyzing acrylonitrile dimerization. The present invention will be described in detail with reference to the following examples and drawings, it should be understood that the examples and drawings are only illustrative of the present invention and are not intended to limit the scope of the present invention in any way, and all reasonable variations and combinations included within the spirit of the present invention fall within the scope of the present invention.
As shown in FIG. 1, wherein R001 is a reactive distillation column, D001 is a condenser, E001 is a reboiler, and C001-C005 is an intermediate condenser. The reactive rectification tower R001 consists of a rectification section, a reaction section and a stripping section, wherein the reaction section is provided with a negative and positive electrode array, and the reaction section and the rectification section are provided with 5 intermediate condensers. Acrylonitrile, supporting electrolyte and aqueous solution are introduced into a reaction rectifying tower R001 from a feeding plate, and dimerization of acrylonitrile at a cathode is carried out to generate adiponitrile at high selectivity, and meanwhile, oxidation of water at an anode is carried out to generate oxygen; and the oxygen is discharged after being cooled by the tower top condenser D001, and heavy components of adiponitrile, water, salt and a small amount of by-products are extracted from a tower kettle reboiler E001. The intercondensers C001-C005 are mainly used for removing heat brought by input electric energy, reducing the load of the overhead condenser D001 and maintaining the change of gas-liquid flow rate in the reaction area within a narrow range.
Example 1
Respectively introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction area, wherein the total feeding amount is 11kg/hr, the AN is 5kg/hr, the dipotassium hydrogen phosphate is 1kg/hr, and the water is 5 kg/hr; the feeding temperature of the reactive distillation tower is 60 ℃, the tower operating pressure is 1.5atm, the tower top temperature is 77.63 ℃, the tower kettle temperature is 110 ℃, the boiling ratio is fixed to 1, the number of theoretical plates is 45, the feeding plate is the 10 th plate above the reaction zone, and the reaction residence time is 5 s; the cathode and anode plates are respectively lead and Ti \ RuO2Material arranged in the area of 11 th to 35 th theoretical plates, and the area of the cathode on the unit tower plate is 24.5m2The cathode potential is fixed to-3.0V vs SCE; the reaction section and the rectifying section of the reaction rectifying tower are provided with 5 intermediate condensers which are respectively positioned on the 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plates (C001-C005), the load of the C001 is-3.25 kW, and the load of the C002-C005 is-2 kW. Warp beamAfter the reaction and rectification, oxygen generated by the anode is discharged through a condenser at the top of the tower, the molar concentration reaches 99%, materials at the bottom of the tower are heated by a reboiler, heavy Adiponitrile (ADN), water, salt and a small amount of by-products are extracted from the bottom of the tower, AN with a medium boiling point is reserved in the reaction and rectification tower until the AN is completely converted, and the AN conversion rate is 98.21%.
Example 2
Respectively introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction area, wherein the total feeding amount is 11kg/hr, the AN is 5kg/hr, the dipotassium hydrogen phosphate is 1kg/hr, and the water is 5 kg/hr; the feeding temperature of the reactive distillation column is 30 ℃, the operating pressure of the reactive distillation column is 1.5atm, the temperature of the top of the column is 78.27 ℃, the temperature of the bottom of the column is 107.01 ℃, the boiling ratio is fixed to be 0.8, the number of theoretical plates is 45, the feeding plate is the 10 th plate above the reaction zone, and the reaction residence time is 5 s; the cathode and anode plates are respectively lead and Ti \ RuO2Material arranged in the area of 11 th to 35 th theoretical plates, and the area of the cathode on the unit tower plate is 30m2The cathode potential is fixed to-3.0V vs SCE; the reaction section and the rectifying section of the reaction rectifying tower are provided with 5 intermediate condensers which are respectively positioned on the 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plates (C001-C005), the load of the C001 is-3.25 kW, and the load of the C002-C005 is-2 kW. After the reaction and rectification, oxygen generated by the anode is discharged through a condenser at the top of the tower, the molar concentration reaches 98%, materials at the bottom of the tower are heated by a reboiler, heavy Adiponitrile (ADN), water, salt and a small amount of by-products are extracted from the bottom of the tower, AN with a medium boiling point is reserved in the reaction and rectification tower until the AN is completely converted, and the AN conversion rate is 99.3%.
Example 3
Respectively introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction area, wherein the total feeding amount is 22kg/hr, the AN is 8kg/hr, the dipotassium hydrogen phosphate is 3kg/hr, and the water is 11 kg/hr; the feeding temperature of the reactive distillation tower is 60 ℃, the tower operating pressure is 1atm, the tower top temperature is 69.8 ℃, the tower kettle temperature is 118.3 ℃, the boiling ratio is fixed to 1, the theoretical plate number is 45, the feeding plate is the 11 th plate, and the reaction residence time is 5 s; the cathode and anode plates are respectively lead and Ti \ RuO2Material arranged in the area of 11 th to 35 th theoretical plates, and the area of the cathode on the unit tower plate is 24.5m2The cathode potential is fixed to-3.0V vs SCE; the reaction section and the rectifying section of the reaction rectifying tower are provided with 5 intermediate condensers which are respectively positioned on the 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plates (C001-C005), the load of the C001 is-3.25 kW, and the load of the C002-C005 is-2 kW. After the reaction and rectification, oxygen generated by the anode is discharged through a condenser at the top of the tower, materials at the bottom of the tower are heated by a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of by-products are extracted from the bottom of the tower, AN with a medium boiling point is reserved in the reaction and rectification tower until the AN is completely converted, and the AN conversion rate is 90.2%.
Example 4
Respectively introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction area, wherein the total feeding amount is 11kg/hr, the AN is 5kg/hr, the dipotassium hydrogen phosphate is 1kg/hr, and the water is 5 kg/hr; the feeding temperature of the reactive distillation tower is 60 ℃, the operating pressure of the tower is 1.5atm, the temperature of the top of the tower is 76.1 ℃, the temperature of the bottom of the tower is 114 ℃, the boiling ratio is fixed to 1, the number of theoretical plates is 55, the feeding plate is a 15 th plate, and the reaction residence time is 5 s; the cathode and anode plates are respectively lead and Ti \ RuO2Material arranged in the area of 16 th to 40 th theoretical plates, and the area of the cathode on the unit tower plate is 30m2The cathode potential is fixed to-3.0V vs SCE; the reaction section and the rectifying section of the reaction rectifying tower are provided with 5 intermediate condensers which are respectively positioned on the 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plates (C001-C005), the load of the C001 is-3.25 kW, and the load of the C002-C005 is-2 kW. After the reaction and rectification, oxygen generated by the anode is discharged through a condenser at the top of the tower, materials at the bottom of the tower are heated by a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of by-products are extracted from the bottom of the tower, AN with a medium boiling point is reserved in the reaction and rectification tower until the AN is completely converted, and the AN conversion rate is 98.27%.
Example 5
Introducing Acrylonitrile (AN) and sodium phosphate aqueous solution into a reactive distillation tower through a feeding plate above a reaction zone respectively, wherein the total feeding amount is 11kg/hr, the AN is 5kg/hr, the sodium phosphate is 1kg/hr, and the water is 5 kg/hr; the feed temperature of the reactive distillation column was 60 deg.CThe tower operating pressure is 1.5atm, the tower top temperature is 73.52 ℃, the tower kettle temperature is 116.7 ℃, the boiling ratio is fixed to 1.5, the theoretical plate number is 45, the feeding plate is the 10 th plate, and the reaction residence time is 5 s; the cathode and anode plates are respectively lead and Ti \ RuO2Material arranged in the region of 10 th to 40 th theoretical plates and having a cathode area of 24.5m per tray2The cathode potential is fixed to-3.0V vs SCE; the reaction section and the rectifying section of the reaction rectifying tower are provided with 5 intermediate condensers which are respectively positioned on the 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plates (C001-C005), the load of the C001 is-3.25 kW, and the load of the C002-C005 is-2 kW. After the reaction and rectification, oxygen generated by the anode is discharged through a condenser at the top of the tower, materials at the bottom of the tower are heated by a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of by-products are extracted from the bottom of the tower, AN with a medium boiling point is reserved in the reaction and rectification tower until the AN is completely converted, and the AN conversion rate is 97.89%.
For the sake of comparative explanation, the material feeding conditions in each example are shown in table 1, the reactive distillation column conditions are shown in table 2, and the reactive distillation results are shown in table 3.
TABLE 1
TABLE 2
TABLE 3
Claims (10)
1. A device and a method for preparing adiponitrile by electrolytic dimerization of acrylonitrile are characterized in that a reactive rectification tower R001 consists of a rectification section, a reaction section and a stripping section, a condenser D001 is arranged at the top of the tower, a reboiler E001 is arranged at the bottom of the tower, and a plurality of negative and positive electrodes are arranged in the reaction section; introducing one or more streams (stream 1) containing acrylonitrile, supporting electrolyte, water and other auxiliary components into a reactive rectification column R001 to produce adiponitrile at high selectivity from acrylonitrile at the cathode and oxygen gas at the oxidation of water at the anode (stream 2); finally, oxygen is discharged via the overhead condenser D001 and the heavy adiponitrile, water, salts and small amounts of by-products are withdrawn from the kettle reboiler E001 (stream 3).
2. The apparatus and process according to claim 1, characterized in that the reaction section and the rectification section are provided with several intermediate condensers.
3. The apparatus and process of claim 1, wherein the mass fraction of acrylonitrile, the mass fraction of supporting electrolyte and the mass fraction of water in the feed stream are in the range of 1% to 90%, 1% to 20% and 10% to 95%.
4. The apparatus and method according to claim 1, wherein the pressure of R001 in the reactive distillation column is 0.5-10 atm, the temperature of the top of the column is-20 ℃, the temperature of the bottom of the column is 90-250 ℃, and the reboiling ratio of the bottom of the column is 0.5-3.
5. The apparatus and method of claim 1, wherein said reactive rectification column R001 comprises 30 to 100 theoretical plates, wherein said rectification section has 5 to 50 theoretical plates.
6. The apparatus and method as claimed in claim 1, wherein the total cathode surface area per acrylonitrile feed flow (1kg/h) in the reactive distillation column R001 is 200-1000 m2The current density is 10 to 10000A/m2。
7. The apparatus and method as claimed in claim 1, wherein the cathode is a mesh material composed of one or more of lead, cadmium and their alloys, and the anode material is stainless steel, Ti \ RuO2、Ti\IrO2Etc. to form a web material.
8. The apparatus and method of claim 1, wherein the cathode and anode are installed in a liquid phase flow region of a reactive distillation column.
9. The apparatus and process according to claim 1, wherein the overhead condenser D001 is a partial condenser and the overhead oxygen withdrawal purity is 90-100%.
10. The device and method according to claim 1, wherein the supporting electrolyte is one or more of phosphate and hydrogen phosphate, preferably dipotassium hydrogen phosphate and sodium phosphate.
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| CN115074761A (en) * | 2022-07-13 | 2022-09-20 | 南京大学 | Method for synthesizing adiponitrile by electrochemical reduction based on microreactor |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1483073A (en) * | 1965-05-19 | 1967-06-02 | Basf Ag | Process for preparing 3-hexenedinitrile |
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