CN112663078B - 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
- Publication number
- CN112663078B CN112663078B CN202011207708.6A CN202011207708A CN112663078B CN 112663078 B CN112663078 B CN 112663078B CN 202011207708 A CN202011207708 A CN 202011207708A CN 112663078 B CN112663078 B CN 112663078B
- Authority
- CN
- China
- Prior art keywords
- reaction
- tower
- acrylonitrile
- adiponitrile
- section
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 29
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 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
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 16
- 238000000066 reactive distillation Methods 0.000 claims description 14
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical group [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 10
- 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
- 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
- 238000007599 discharging Methods 0.000 claims 1
- -1 ti\ruo 2 Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 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
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 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
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 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
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 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
- 239000000243 solution Substances 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
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本发明属于己二腈的制备技术领域，具体涉及一种将丙烯腈电解反应集成到反应精馏塔中制备己二腈的装置和方法。反应精馏塔由精馏段、反应段和提馏段组成，在塔顶、反应段和精馏段设置冷凝器，塔底设置再沸器，反应段设置阴阳电极阵列；丙烯腈、支持电解质、水及其它辅助组分引入反应精馏塔中后，在阴极丙烯腈高选择性生成己二腈，同时在阳极水氧化生成氧气；最终氧气经塔顶排出，重组分己二腈、水、盐和少量副产物从塔釜采出。本发明将丙烯腈的电解二聚反应集成到反应精馏塔中，解决了普通平行板式电解槽中丙烯腈单程转化率低、选择性差和阳极析氧造成的反应物流体积膨胀等问题，丙烯腈转化率可高达99％，得到的己二腈选择性大于95％。
The present invention belongs to the technical field of preparation of adiponitrile, and specifically relates to a device and method for preparing adiponitrile by integrating electrolytic reaction of acrylonitrile into a reaction distillation tower. The reaction distillation tower is composed of a distillation section, a reaction section and a stripping section. Condensers are arranged at the top of the tower, the reaction section and the distillation section, a reboiler is arranged at the bottom of the tower, and an array of positive and negative electrodes is arranged in the reaction section. After acrylonitrile, a supporting electrolyte, water and other auxiliary components are introduced into the reaction distillation tower, acrylonitrile is highly selectively generated into adiponitrile at the cathode, and water is oxidized at the anode to generate oxygen. Finally, oxygen is discharged through the top of the tower, and heavy components adiponitrile, water, salt and a small amount of by-products are extracted from the bottom of the tower. The present invention integrates the electrolytic dimerization reaction of acrylonitrile into the reaction distillation tower, solves the problems of low single-pass conversion rate and poor selectivity of acrylonitrile in ordinary parallel plate electrolyzers, and the volume expansion of the reactant flow caused by oxygen evolution at the anode, and the conversion rate of acrylonitrile can be as high as 99%, and the selectivity of adiponitrile obtained is greater than 95%.
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) is also called 1, 4-dicyanobutane, is an important chemical raw material, is mainly used for preparing an intermediate hexamethylenediamine of polyamide nylon 6, can be used for preparing rubber additives, pesticides, bactericides and high polymer materials, can also be used as plasticizers, textile additives, solvents, extractants and the like, and has wide application.
At present, adiponitrile (ADN) is prepared industrially mainly by thermochemical catalytic cyanation of 1, 3-butadiene or electrochemical dimerization of Acrylonitrile (AN), wherein the electrochemical dimerization is less toxic, environmentally friendly and requires only one step of reaction compared to the conventional butadiene method, and thus is more sustainable and competitive in the future.
The process of the electrolytic dimerization of Acrylonitrile (AN) was first successfully developed by the company Meng Shandou in the us in the 60 s of the 20 th century, with great practical significance, and many methods for carrying out this reaction have been developed nowadays, such as electrolysis cells separated by a membrane or electrolysis in undivided cells. Among them patent US3193475, US3193481, US3616319, US3335162 disclose a process for the dimerization of AN in diaphragm-separated cells which is attractive enough to be used industrially for a long time but requires a high electrolysis energy consumption, the cell structure is often complex and requires a timed replacement of the diaphragm. Compared with the electrolytic cell separated by the diaphragm, the undivided electrolytic cell has simple design, low cell voltage and easy operation in industry, and is a direct electrosynthesis process. As in patent US3898140, US3689382 discloses a process for the preparation of adiponitrile by electrolysis of AN aqueous solution in a diaphragm-free electrolytic cell, and later patent US4789442 further improves the reaction efficiency by electrolysis of AN emulsion consisting of AN aqueous phase and AN organic phase on a lead or lead alloy cathode. The german basf company also uses a special capillary gap electrolyzer (patent US 3616320) to build a diaphragm-free electrolyzer, and reduces the ohmic drop of solution and energy consumption by reducing the electrode gap to form a capillary gap reactor for film electrolyte, but like other electrolysis processes, electrochemical reduction or oxidation reaction can only occur on parallel plate type cathode or anode walls respectively, the electrode area corresponding to the unit volume of reaction liquid is small, so the conversion per pass AN is low, the outlet liquid needs to recover AN through a large number of separation operations and recycle the AN to the electrolyzer, and the operation difficulty and cost are increased. If the conversion is simply increased by increasing the current density or the electrode area, the by-product increases due to the decrease of the AN concentration in the latter period of the reaction, and the process performance is lowered instead. In addition, when the anode generates half mole of oxygen gas per 1 mole of ADN generated from the cathode, the volume of the reactant flow between the electrode plates is greatly expanded at a high conversion rate, which reduces the local residence time and prevents the electrolyte solution from contacting the electrode, thus making the operation difficult.
In order to overcome the defects of the traditional electrolytic tank in the ADN electrolytic synthesis process, further improve the conversion rate of AN, reduce the separation procedure and the occurrence of byproducts, and continuously remove the gaseous oxygen in the emulsion at the same time, a new process for preparing the ADN by electrolyzing AN is required to be sought.
Disclosure of Invention
The invention aims to provide a device and a method for preparing Adiponitrile (ADN) by integrating AN electrolytic reaction into a reaction rectifying tower, overcome the defects in the existing Acrylonitrile (AN) electrolytic dimerization process, provide a process for preparing adiponitrile by integrating the electrolytic reaction and phase separation, reduce the cost, improve the conversion rate of Acrylonitrile (AN) and obtain AN Adiponitrile (ADN) product with high selectivity.
A device and a method for preparing adiponitrile by electrolytic dimerization of acrylonitrile, which comprises a reaction rectifying tower R001, a supporting electrolyte, water and other auxiliary components, wherein the reaction rectifying tower R001 consists of a rectifying section, a reaction section and a stripping section, a condenser D001 is arranged at the top of the reaction rectifying tower, a reboiler E001 is arranged at the bottom of the reaction rectifying tower, a plurality of negative and positive electrodes are arranged in the reaction section, one or a plurality of material flows containing the acrylonitrile, the supporting electrolyte, the water and the other auxiliary components are introduced into the reaction rectifying tower R001, the adiponitrile is formed at the cathode in a high selectivity mode, meanwhile, oxygen is formed at the anode water in an oxidizing mode, the final oxygen is discharged through the condenser D001 at the top of the reaction rectifying tower, and heavy components adiponitrile, water, salt and a small amount of byproducts are extracted from the reboiler E001 at the bottom of the reaction rectifying 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 in the feed material flow is 1% -90%, the mass fraction of supporting electrolyte is 1% -20%, and the mass fraction of water is 10% -95%.
The pressure of the reaction rectifying tower R001 is 0.5-10 atm, the temperature of the tower top is-20 ℃, the temperature of the tower bottom is 90-250 ℃, and the reboiling ratio of the tower bottom is 0.5-3.
The reactive rectifying tower R001 is provided with 30-100 theoretical plates, wherein the rectifying section is provided with 5-50 theoretical plates, and the position of the feeding plate is 10-21 theoretical plates.
The total surface area of the cathode corresponding to the unit acrylonitrile feeding flow (1 kg/h) in the reactive rectifying tower R001 is 200-1000 m 2, and the current density is 10-10000A/m 2.
The cathode is a reticular material formed by one or more of lead, cadmium and alloys thereof, and the anode material is a reticular material formed by stainless steel, ti\RuO 2、Ti\IrO2 and the like.
The cathode and the anode are arranged in the liquid phase flow area of the reaction rectifying tower 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 electrolytic dimerization reaction of the acrylonitrile 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 single pass conversion rate of the acrylonitrile, volume expansion of the reactor caused by the anodic oxygen evolution reaction and the like in a common parallel plate type electrolytic tank 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 cost are reduced. The reactive rectifying tower is provided 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 rate in the reaction zone can be kept in a narrower range, thereby being beneficial to the design operation of the rectifying tower and the uniform occurrence of electrolytic reaction.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus for preparing adiponitrile by electrolyzing acrylonitrile dimerization in accordance with the present invention.
Detailed Description
The invention aims to provide a novel device and a method for preparing adiponitrile by electrolyzing acrylonitrile dimerization. The invention will now be described in detail with reference to the examples and the accompanying drawings, it being understood that the examples and the accompanying drawings are only illustrative of the invention and are not intended to limit the scope of the invention in any way, and that all reasonable variations and combinations included within the scope of the invention are within the scope of the invention.
As shown in FIG. 1, R001 is a reactive rectifying tower, D001 is a condenser, E001 is a reboiler, and C001-C005 is an intermediate condenser. The reactive rectifying tower R001 consists of a rectifying section, a reaction section and a stripping section, wherein the reaction section is provided with a cathode-anode electrode array, and the reaction section and the rectifying section are provided with 5 intermediate condensers. Acrylonitrile, supporting electrolyte and aqueous solution are introduced into a reactive rectifying tower R001 from a feeding plate, adiponitrile is formed in high selectivity in cathode acrylonitrile dimerization, meanwhile oxygen is formed in anode water oxidation, the oxygen is discharged after being cooled by a tower top condenser D001, and heavy components adiponitrile, water, salt and a small amount of byproducts are extracted from a tower kettle reboiler E001. The intercondensers C001-C005 are mainly used for removing heat caused by input electric energy, reducing the load of the tower top condenser D001 and keeping the change of the gas-liquid flow rate of the reaction zone within a narrow range.
Example 1
Introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction zone, wherein the total feeding amount is 11kg/hr, AN is 5kg/hr, dipotassium hydrogen phosphate is 1kg/hr, water is 5kg/hr, the feeding temperature of the reaction rectifying tower is 60 ℃, the operating pressure of the tower is 1.5atm, the tower top temperature is 77.63 ℃, the tower kettle temperature is 110 ℃, the boiling ratio is fixed to be 1, the theoretical plate number is 45, the feeding plate is the 10 th plate above the reaction zone, the reaction residence time is 5 seconds, the cathode and anode plates are respectively made of lead and Ti/RuO 2 materials, the cathode and anode plates are respectively arranged in the 11 th to 35 th theoretical plate areas, the cathode area on the unit plate is 24.5m 2, the cathode potential is fixed to be-3.0V vs SCE, 5 intermediate condensers are respectively arranged in the reaction section and the rectifying section of the reaction rectifying tower, the theoretical plates (C001-C005) are respectively positioned at 5,10,15,20,25,30 and C001-C005 and the load is 25-3.25 kW-2. After reactive distillation, oxygen generated by AN anode is discharged through a tower top condenser, the molar concentration reaches 99%, a tower bottom material is heated through a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of byproduct tower bottoms are extracted, AN with medium boiling point is reserved in the reactive distillation tower until complete conversion, and AN conversion rate is 98.21%.
Example 2
Introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction zone respectively, wherein the total feeding amount is 11kg/hr, AN is 5kg/hr, dipotassium hydrogen phosphate is 1kg/hr, water is 5kg/hr, the feeding temperature of the reaction rectifying tower is 30 ℃, the operating pressure of the tower is 1.5atm, the tower top temperature is 78.27 ℃, the tower bottom temperature is 107.01 ℃, the boiling ratio is fixed to 0.8, the theoretical plate number is 45, the feeding plate is a10 th plate above the reaction zone, the reaction residence time is 5s, the cathode and anode plates are respectively made of lead and Ti/RuO 2 materials, the cathode and anode plates are respectively arranged in the 11 th-35 th theoretical plate area, the cathode area on the unit plate is 30m 2, the cathode potential is fixed to-3.0V vs SCE, 5 intermediate condensers are respectively arranged in the reaction section and the rectifying section of the reaction rectifying tower, the theoretical plate is 5 th, 10 th, 15 th, 20 th, 25 th and 30 th theoretical plate (C001-C005) and the load of C001-3.002-3.25 kW is respectively 2-005. After reactive distillation, oxygen generated by AN anode is discharged through a tower top condenser, the molar concentration reaches 98%, a tower bottom material is heated through a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of byproducts are extracted from the tower bottom, AN with medium boiling point is reserved in the reactive distillation tower until complete conversion is achieved, and AN conversion rate is 99.3%.
Example 3
Introducing Acrylonitrile (AN), dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction zone, wherein the total feeding amount is 22kg/hr, AN is 8kg/hr, dipotassium hydrogen phosphate is 3kg/hr, water is 11kg/hr, the feeding temperature of the reaction rectifying tower is 60 ℃, the operating pressure of the tower is 1atm, the top temperature of the tower is 69.8 ℃, the temperature of the tower kettle is 118.3 ℃, the boiling ratio is fixed to be 1, the theoretical plate number is 45, the feeding plate is 11 th plate, the reaction residence time is 5s, the cathode and anode plates are respectively made of lead and Ti/RuO 2 materials, the cathode and anode plates are arranged in 11-35 theoretical plate areas, the cathode area on the unit plate is 24.5m 2, the cathode potential is fixed to be-3.0V vs SCE, 5 intermediate condensers are arranged in the reaction section and the rectifying section of the reaction rectifying tower, and are respectively positioned in 5,10,15,20,25,30 theoretical plates (C001-C005), and the load of C001 is-3.25kW-2-002 C.002 respectively. After reactive distillation, oxygen generated by AN anode is discharged through a tower top condenser, a tower bottom material is heated through a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of byproducts are extracted from the tower bottom, AN with medium boiling point is reserved in the reactive distillation tower until complete conversion is achieved, and AN conversion rate is 90.2%.
Example 4
Introducing Acrylonitrile (AN) and dipotassium hydrogen phosphate aqueous solution into a reaction rectifying tower through a feeding plate above a reaction zone respectively, wherein the total feeding amount is 11kg/hr, AN is 5kg/hr, dipotassium hydrogen phosphate is 1kg/hr, water is 5kg/hr, the feeding temperature of the reaction rectifying tower is 60 ℃, the operating pressure of the tower is 1.5atm, the tower top temperature is 76.1 ℃, the tower kettle temperature is 114 ℃, the boiling ratio is fixed to be 1, the theoretical plate number is 55, the feeding plate is 15 th plate, the reaction residence time is 5s, the cathode and anode plates are respectively made of lead and Ti/RuO 2 materials and are arranged in 16-40 th theoretical plate areas, the cathode area on the unit plate is 30m 2, the cathode potential is fixed to be-3.0V vs SCE, 5 intermediate condensers are arranged in the reaction section and the rectifying section of the reaction rectifying tower respectively, the load of-3.25, 30 theoretical plates (C001-C005) is-3.25 kW, and the load of C001-3.25-C002 is-2 kW respectively. After reactive distillation, oxygen generated by AN anode is discharged through a tower top condenser, a tower bottom material is heated through a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of byproducts are extracted from the tower bottom, AN with medium boiling point is reserved in the reactive distillation tower until complete conversion is achieved, and AN conversion rate is 98.27%.
Example 5
Acrylonitrile (AN), sodium phosphate aqueous solution are respectively introduced into a reactive rectifying tower through a feeding plate above a reaction zone, the total feeding amount is 11kg/hr, wherein AN is 5kg/hr, sodium phosphate is 1kg/hr, water is 5kg/hr, the feeding temperature of the reactive rectifying tower is 60 ℃, the operating pressure of the tower is 1.5atm, the tower top temperature is 73.52 ℃, the tower bottom temperature is 116.7 ℃, the boiling ratio is fixed to be 1.5, the theoretical plate number is 45, the feeding plate is 10 th plate, the reaction residence time is 5s, the cathode and anode plates are respectively lead and Ti/RuO 2 materials and are arranged in 10-40 th theoretical plate areas, the cathode area on the unit plate is 24.5m 2, the cathode potential is fixed to be-3.0V vs SCE, 5 intermediate condensers are respectively arranged in a reactive rectifying tower reaction section and a rectifying section, and are respectively positioned in 5,10,15,20,25,30 theoretical plates (C001-C005), and the load of C001 is-3.25 kW and the load of C002-2 kW is respectively arranged in the reactive rectifying tower. After reactive distillation, oxygen generated by AN anode is discharged through a tower top condenser, a tower bottom material is heated through a reboiler, heavy component Adiponitrile (ADN), water, salt and a small amount of byproducts are extracted from the tower bottom, AN with medium boiling point is reserved in the reactive distillation tower until complete conversion is achieved, and AN conversion rate is 97.89%.
For ease of comparison, the feed conditions for each example are shown in Table 1, the reaction distillation column conditions are shown in Table 2, and the reaction distillation results are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3 Table 3
Claims (10)
1. A process for producing adiponitrile by electrolytic dimerization of acrylonitrile, which comprises introducing one or more streams containing acrylonitrile, supporting electrolyte, water and other auxiliary components into a reactive distillation column (R001), forming adiponitrile with high selectivity at the cathode acrylonitrile and oxygen at the anode water, discharging the final oxygen through a top condenser (D001), and withdrawing heavy components adiponitrile, water, salt and a small amount of by-products from a column bottom reboiler (E001);
The reaction rectifying tower consists of a rectifying section, a reaction section and a stripping section, wherein a condenser (D001) is arranged at the top of the tower, a reboiler (E001) is arranged at the bottom of the tower, a plurality of negative and positive electrodes and a plurality of intermediate condensers are arranged at the reaction section, a plurality of intermediate condensers are arranged at the stripping section, the reaction rectifying tower (R001) comprises 45-100 theoretical plates, 5-50 theoretical plates are arranged at the rectifying section, 10-21 theoretical plates are arranged at the feeding plate position, and the negative electrode and the positive electrode polar plates are arranged in 16-40 theoretical plate areas.
2. The method of claim 1, wherein the cathode of the anode and cathode is a mesh material composed of one or more of lead, cadmium and alloys thereof, and the anode is a mesh material composed of one or more of stainless steel, ti\ruo 2、Ti\IrO2.
3. The method of claim 1, wherein the cathode and anode are installed in a liquid phase flow region of a reactive distillation column.
4. The method according to claim 1, characterized in that the overhead condenser (D001) is a partial condenser.
5. The method according to claim 1, wherein the acrylonitrile mass fraction is 1-90%, the supporting electrolyte mass fraction is 1-20% and the water mass fraction is 10-95% in the stream introduced into the reactive distillation column (R001).
6. The method according to claim 1, wherein the pressure of the reactive rectifying column (R001) 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.
7. The method according to claim 6, wherein the total surface area of the cathode per unit acrylonitrile feed rate in the reactive distillation column (R001) is 200-1000 m 2, and the current density is 10-10000A/m 2.
8. The method of claim 1, wherein the overhead oxygen take-off purity is 90-100%.
9. The method of claim 1, wherein the supporting electrolyte is one or more of a phosphate, hydrogen phosphate.
10. The method of claim 9, wherein the supporting electrolyte is dipotassium hydrogen phosphate and sodium phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011207708.6A CN112663078B (en) | 2020-11-03 | 2020-11-03 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011207708.6A CN112663078B (en) | 2020-11-03 | 2020-11-03 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112663078A CN112663078A (en) | 2021-04-16 |
| CN112663078B true CN112663078B (en) | 2024-12-27 |
Family
ID=75402842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011207708.6A Active CN112663078B (en) | 2020-11-03 | 2020-11-03 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112663078B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074761B (en) * | 2022-07-13 | 2023-12-26 | 南京大学 | Method for synthesizing adiponitrile by electrochemical reduction based on microreactor |
| CN118756173B (en) * | 2024-09-05 | 2024-11-26 | 万华化学集团股份有限公司 | Device and method for preparing diacetal by electrolyzing p-methylanisole |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
| CN102398894A (en) * | 2010-09-07 | 2012-04-04 | 廖文加 | Preparation of deuterium-depleted water, and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3267131A (en) * | 1964-04-27 | 1966-08-16 | Monsanto Co | Product separation and recovery in adiponitrile manufacture |
| FR1483073A (en) * | 1965-05-19 | 1967-06-02 | Basf Ag | Process for preparing 3-hexenedinitrile |
| US3597331A (en) * | 1966-11-16 | 1971-08-03 | Asahi Chemical Ind | Process for the recovery of adiponitrile from an electrolytic hydrodimerization by directly distilling the catholyte emulsion |
| CN102400174B (en) * | 2011-11-30 | 2014-07-16 | 青岛双瑞海洋环境工程股份有限公司 | Novel device for preparing adiponitrile by electrolyzing acrylonitrile dimer |
| EP2985364A1 (en) * | 2014-08-14 | 2016-02-17 | Basf Se | Process for preparing alcohols by electrochemical reductive coupling |
| CN105367368B (en) * | 2014-08-27 | 2017-08-11 | 中国石油化工股份有限公司 | The method that high-purity isobutylene is prepared from C_4 hydrocarbon |
| FR3025523B1 (en) * | 2014-09-04 | 2016-10-28 | Solios Chemical | METHOD FOR DISTILLATION OF HARD TAR AND DEVICE FOR ITS IMPLEMENTATION |
| CN107118106B (en) * | 2017-06-20 | 2019-06-21 | 陕西延长石油（集团）有限责任公司 | A kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis |
| CN108517536B (en) * | 2018-07-09 | 2019-06-28 | 中国石油大学(华东) | A method of for being electrolysed, acrylonitrile dimerization prepares the electrolyte of adiponitrile and electrolysis acrylonitrile dimerization prepares adiponitrile |
| CN109678756B (en) * | 2018-12-25 | 2021-09-17 | 上海交通大学 | Reaction device and method for producing adiponitrile |
| CN110042422A (en) * | 2019-04-30 | 2019-07-23 | 青岛中石恒润化工技术有限公司 | A method of for Synthetic Method of Adiponitrile From Electrolytic Dimeric Acrylonitrile |
-
2020
- 2020-11-03 CN CN202011207708.6A patent/CN112663078B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102398894A (en) * | 2010-09-07 | 2012-04-04 | 廖文加 | Preparation of deuterium-depleted water, and application thereof |
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112663078A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11131028B2 (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| CA2950294C (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| EP3149228B1 (en) | Method for electrochemical reduction of carbon dioxide employing a gas diffusion electrode | |
| DK2898117T3 (en) | Integrated process for the production of oxalic acid from carbon dioxide | |
| EP3234226B1 (en) | Method for manufacturing 2,3-butanediol | |
| CN112663078B (en) | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile | |
| US20170121831A1 (en) | Integrated Process for Co-Production of Carboxylic Acids and Halogen Products from Carbon Dioxide | |
| WO2011120441A1 (en) | Paired electrosynthetic method for producing butanedioic acid and sulfuric acid | |
| US6909016B2 (en) | Production of butane tetracarboxylic acid derivative by means of coupled electrosynthesis | |
| CN112626547A (en) | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance | |
| CN107118106A (en) | A kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination ammonolysis | |
| CN115074761B (en) | Method for synthesizing adiponitrile by electrochemical reduction based on microreactor | |
| Scott | Industrial electrochemical synthesis processes: recent developments in reactor design | |
| CN103938220B (en) | Electrolysis prepares method and the electrolysis unit of hydrodiazo benzene-like compounds | |
| EP3854910A1 (en) | Electrochemical production of formaldehyde | |
| Li et al. | The paired electrochemical synthesis of gluconic acid and sorbitol | |
| JP2006037233A (en) | Preparation method of 2-alkyne-1-acetal | |
| EP3512982B1 (en) | Electrochemical method for manufacturing methyl ethyl ketone | |
| CN105063655B (en) | The method for producing iminodiacetic acid | |
| Electrochemical know-how et al. | Industrial Electroorganic Chemistry | |
| CN115717250A (en) | Electrochemical method for paired preparation of butanediol and vanillin | |
| CN1238564C (en) | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed | |
| CN117867532A (en) | A method for synthesizing p-aminophenol and its application | |
| CN118756173A (en) | A device and method for preparing diacetal by electrolysis of p-methyl anisole | |
| CN119372667A (en) | Method and device for producing formic acid and hydrogen by electrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |