CN111574399A - Reaction system and method for ammoximation and recovery of tert-butyl alcohol - Google Patents
Reaction system and method for ammoximation and recovery of tert-butyl alcohol Download PDFInfo
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- CN111574399A CN111574399A CN202010284848.7A CN202010284848A CN111574399A CN 111574399 A CN111574399 A CN 111574399A CN 202010284848 A CN202010284848 A CN 202010284848A CN 111574399 A CN111574399 A CN 111574399A
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 267
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 91
- 238000011084 recovery Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000006146 oximation reaction Methods 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000010992 reflux Methods 0.000 claims abstract description 56
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 51
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 71
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 28
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 24
- 229910021529 ammonia Inorganic materials 0.000 description 17
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a reaction system and a method for ammoximation and recovery of tert-butyl alcohol, which comprises an oximation reactor, a reaction clear liquid buffer tank, a tail gas absorption tower, a tert-butyl alcohol recovery tower and a tert-butyl alcohol reflux tank, wherein the top of the oximation reactor is provided with a tail gas outlet, the bottom of the oximation reactor is provided with a discharge port, the discharge port is connected with the reaction clear liquid buffer tank, the tail gas outlet is connected with the tail gas absorption tower, materials discharged from the reaction clear liquid buffer tank are introduced from the middle section of the tert-butyl alcohol recovery tower, the top of the tert-butyl alcohol recovery tower is connected with the tert-butyl alcohol reflux tank, an external circulation heat exchange device is arranged outside the oximation reactor, and a micro-interface generator is arranged inside the oximation reactor and used for. According to the reaction system for ammoximation and recovery of tert-butyl alcohol, the micro-interface generator is arranged in the reactor, so that the mass transfer area of a gas-liquid phase is increased, and the reaction temperature and pressure are reduced, so that the side reaction is inhibited, and the oximation reaction efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of intensified reactions, and particularly relates to a reaction system and a method for ammoximation and recovery of tert-butyl alcohol.
Background
Caprolactam is an important organic compound, and downstream products of caprolactam are widely applied to the industries of spinning, tires, food packaging and the like. The production process mostly adopts ammoximation to produce cyclohexanone oxime, and then liquid phase rearrangement is carried out to produce caprolactam, and the ammoximation reaction of the cyclohexanone is a core control program in the process. In the cyclohexanone ammoximation reaction process, factors influencing the reaction mainly comprise mass transfer efficiency, reaction temperature and pressure, reaction time, catalyst concentration and raw material ratio and the like, and researches show that the mass transfer efficiency and the reaction temperature and pressure have great influence on production; on the other hand, the oximation reaction is a strong exothermic reaction, the temperature and the pressure are too high, the decomposition products of cyclohexanone and cyclohexanone oxime are increased, and the products are not easy to remove in the post-process, and the yield and the quality of the final product caprolactam are influenced.
In conclusion, in order to improve the efficiency of the oximation reaction, reduce the reaction temperature and pressure and reduce the occurrence of side reactions, the improvement of the ammoximation industrialization device is a problem which needs to be solved urgently to reduce the ammoximation cost and improve the ammoximation production load.
Disclosure of Invention
In view of the above, the first objective of the present invention is to provide a reaction system for ammoximation and recovery of tert-butanol, the reaction system is provided with a micro-interface generator inside the ammoximation reactor, and after the micro-interface generator is provided, on one hand, ammonia gas can be dispersed and crushed into micro-bubbles with micron-sized diameters, and the phase interface area between ammonia gas and liquid phase materials is increased, so that the mass transfer space is fully satisfied, the residence time of ammonia gas in the liquid phase is increased, and the consumption of ammonia gas is reduced, thereby greatly improving the efficiency of the ammoximation reaction, effectively inhibiting side reactions, and significantly reducing the energy consumption in the reaction process; on the other hand, the reaction temperature and pressure are reduced, the decomposition products of cyclohexanone and cyclohexanone oxime are reduced, the yield and quality of the final product caprolactam are improved, the energy consumption is reduced, and the system safety is improved.
The second purpose of the invention is to provide a method for carrying out reaction by adopting the reaction system, the method has mild operation conditions, reduces the temperature and pressure of oximation reaction while ensuring the reaction efficiency, has high safety performance and low energy consumption, and achieves better reaction effect than the prior art.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a reaction system for ammoximation and recovery of tertiary butanol, which is characterized by comprising an oximation reactor, a reaction clear liquid buffer tank, a tail gas absorption tower, a tertiary butanol recovery tower and a tertiary butanol reflux tank, wherein,
a tail gas outlet is formed in the top of the oximation reactor, a discharge hole is formed in the bottom of the oximation reactor, the discharge hole is connected with the reaction clear liquid buffer tank, the tail gas outlet is connected with the tail gas absorption tower, materials from the reaction clear liquid buffer tank are introduced from the middle section of the tert-butyl alcohol recovery tower to be used for recovering tert-butyl alcohol, and the top of the tert-butyl alcohol recovery tower is connected with the tert-butyl alcohol reflux tank to be used for gas-liquid separation;
an external circulation heat exchange device is arranged outside the oximation reactor and is used for controlling the temperature inside the oximation reactor; the interior of the oximation reactor is provided with a micro-interface generator which is used for dispersing the broken gas into micro-bubbles with the diameter of micron level.
In the prior art, the cyclohexanone ammoximation reaction has the following problems: on one hand, the gas-liquid phase mass transfer area of the existing oximation reactor is limited, the reaction mixed raw materials and ammonia gas cannot be fully mixed in the reaction process, so that the cyclohexanone is incompletely converted, the oximation conversion rate is low, and the occurrence of side reactions is increased; on the other hand, the ammoximation reaction is a strong exothermic reaction, the temperature is too high, the decomposition products of cyclohexanone and cyclohexanone oxime are increased, and the products are not easy to remove in the post-process, thereby influencing the yield and the quality of the final product caprolactam. According to the reaction system for ammoximation and recovery of tert-butyl alcohol, provided by the invention, after the micro-interface generator is arranged in the oximation reactor, on one hand, ammonia gas can be dispersed and crushed into micro-bubbles with micron-sized diameters, and the phase interface area between the ammonia gas and a liquid-phase material is increased, so that the mass transfer space is fully satisfied, the retention time of the ammonia gas in the liquid phase is increased, and the consumption of the ammonia gas is reduced, thereby greatly improving the oximation reaction efficiency, effectively inhibiting side reactions and remarkably reducing the energy consumption in the reaction process; on the other hand, the reaction temperature and pressure are reduced, the decomposition products of cyclohexanone and cyclohexanone oxime are reduced, the yield and quality of the final product caprolactam are improved, the energy consumption is reduced, and the system safety is improved.
Furthermore, the side wall of the oximation reactor is provided with an air inlet for introducing raw material ammonia, the air inlet extends into the micro-interface generator through a pipeline, the type of the micro-interface generator is a pneumatic micro-interface generator, the number of the micro-interface generators is more than one, and the micro-interface generators are connected in parallel. The ammonia is dispersed and broken into micron-level microbubbles inside the pneumatic micro-interface generator, so that the mass transfer area between the ammonia and the liquid-phase material is effectively increased, the mass transfer resistance is reduced, and the reaction efficiency is improved. In addition, a plurality of the micro-interface generators can be arranged inside the oximation reactor in a series connection mode or a series-parallel mixed connection mode. More preferably, the micro-interface generator is connected to a pipe by welding, threads, or flanges, the pipe being fixed inside the oximation reactor. In addition, the structure of the micro-interface generator is in the prior art, so the specific structure of the micro-interface generator is not the protection focus of the invention.
Further, a liquid inlet and a gas inlet are respectively arranged at the middle section of the tert-butyl alcohol recovery tower, and the liquid inlet is connected with the bottom of the reaction clear liquid buffer tank; the gas inlet is connected with the top of the reaction clear liquid buffer tank. The liquid in the reaction clear liquid buffer tank enters the tertiary butanol recovery tower from the liquid inlet, and the gas in the reaction clear liquid buffer tank enters the tertiary butanol recovery tower from the gas inlet, so that the gas inlet and the liquid inlet are arranged at the same time, because the material components in the reaction clear liquid buffer tank are relatively complex, most of the tertiary butanol exists in a liquid state, and a small amount of the tertiary butanol exists in a reaction product in a gaseous state, and the arrangement of the gas inlet and the liquid inlet is a double-material inlet, so that the tertiary butanol can be fully recovered and utilized.
Preferably, a liquid level-flow cascade control system can be arranged on a pipeline between the liquid inlet and the reaction clear liquid buffer tank, and compared with simple single-loop control, the liquid level-flow cascade control system can achieve a better control effect only by using a conventional instrument, and the liquid level instrument in the liquid level-flow cascade control system can select a pressure transmitter and the flow instrument can select a turbine flowmeter. Further, a tower top condenser is arranged at the tower top of the tertiary butanol recovery tower, and a tower kettle reboiler is arranged at the tower kettle. In order to achieve a better condensation effect, two tower top condensers can be connected in series at the tower top, the first-stage tower top condenser adopts circulating cooling water for condensation, and the second-stage tower top condenser adopts frozen brine for condensation. More preferably, in order to avoid the hydrolysis of cyclohexanone oxime into cyclohexanone at high temperature, the tower reboiler adopts a once-through thermosiphon reboiler to reduce the high-temperature retention time of oxime water.
Furthermore, the reaction system also comprises a return pipeline, wherein one end of the return pipeline is connected with the top of the tertiary butanol recovery tower, and the other end of the return pipeline is connected with the bottom of the tertiary butanol return tank so as to return substances in the tertiary butanol return tank to continue to be separated and purified; the reflux pipeline is provided with a reflux pump, a part of condensate enters the reflux pipeline after being pressurized by the reflux pump to be taken as tower top reflux so as to be used for absorbing the tertiary butanol to recover the excessive heat at the tower top, maintain the heat balance of the whole tower, and can improve the recovery purity of the tertiary butanol after multiple times of reflux. Compared with natural reflux, the reflux pump can adjust the reflux amount, so that the reflux amount is stable and the operability is good.
Furthermore, an exhaust gas cooler is arranged on a pipeline connected with the tail gas outlet and the tail gas absorption tower, a non-condensable gas outlet is arranged on the tertiary butanol reflux tank, and the non-condensable gas outlet is connected with the exhaust gas cooler, so that the non-condensable gas and the tail gas are mixed and then enter the tail gas absorption tower for recycling. Through setting up the exhaust gas cooler and can cooling noncondensable gas, improved the utilization ratio of on-spot tail gas recovery, saved the energy. And cooling the mixed fraction containing water, ammonia, tertiary butanol and the like distilled from the top of the tertiary butanol recovery tower by a tower top condenser, then feeding the cooled mixed fraction into a tertiary butanol reflux tank, mixing the non-condensable gas which is not cooled in the middle with tail gas by an exhaust gas cooler, and then feeding the mixed fraction into a tail gas absorption tower for ammonia recovery.
Further, the tertiary butanol recovery column is of the type of a vertical sieve tray column. Impurities such as cyclohexanone, cyclohexanol, cyclohexanone oxime and the like in the circulating tertiary butanol are much higher in boiling point than the tertiary butanol, so that the separation is easy; however, the boiling point of part of impurities is close to that of the tertiary butanol, so that the separation is difficult, the tertiary butanol recovery tower provided by the invention adopts a vertical sieve plate tower, has the characteristics of high mass transfer space utilization rate and good mass transfer effect, can effectively solve the problem of high difficulty in separating the light impurities of the tertiary butanol, and adopts a reasonable reflux ratio and a reasonable feeding position to improve the removal efficiency of the light impurities of the tertiary butanol in operation.
Furthermore, the bottom end of the inside of the tert-butyl alcohol recovery tower is arranged into a conical hopper shape, so that only recovered tert-butyl alcohol can be received, and the arrangement mode can better separate cyclohexanone oxime from tert-butyl alcohol, thereby improving the recovery efficiency of tert-butyl alcohol and improving the purity of tert-butyl alcohol.
Furthermore, the reaction system also comprises a circulating tertiary butanol tank, the top of the circulating tertiary butanol tank is connected with the bottom of the tertiary butanol reflux tank, and the bottom of the circulating tertiary butanol tank is connected with the bottom of the oximation reactor, so that the tertiary butanol can be reused as the reaction solvent. A small part of condensate in the tertiary butanol reflux tank is used as tower top reflux, the rest of condensate enters the oximation reactor through the circulating tertiary butanol tank to be reused as reaction solvent, the use cost of the tertiary butanol is reduced, and the circulating tertiary butanol tank can be provided with automatic spray condensate water, so that the temperature in the tank can be kept constant.
In addition, the invention also provides a method for oximation reaction and recovery of tert-butyl alcohol, which comprises the following steps:
after ammonia gas is dispersed and crushed into micro bubbles, the micro bubbles and liquid-phase materials are subjected to catalytic oximation reaction; in the process of carrying out the catalytic oximation reaction, the gas which is not completely reacted is recycled, and the tertiary butanol in the reaction product is recycled after the reaction product is collected in a clear liquid manner.
Further, firstly, introducing a liquid-phase material (comprising cyclohexanone, hydrogen peroxide and tert-butyl alcohol) into the oximation reactor, simultaneously introducing ammonia gas into a micro-interface generator arranged in the oximation reactor, so that the ammonia gas is crushed into micro-bubbles with the diameter of micron level, and after the ammonia gas is dispersed and crushed into the micro-bubbles, carrying out catalytic oximation reaction with the liquid-phase material.
In the catalytic oximation reaction process, the unreacted gas is recycled, the reaction product is collected in a clear liquid mode, enters a reaction clear liquid buffer tank through a discharge port, then enters the tower through a liquid inlet and a gas inlet of a tert-butyl alcohol recovery tower respectively, the tert-butyl alcohol in the reaction product is recovered, and the recovered tert-butyl alcohol enters the oximation reactor again and is used as a reaction solvent.
Furthermore, the temperature of the oximation reaction is 80-82 ℃, and the pressure is 0.18-0.23 MPa.
Compared with the prior art, the invention has the beneficial effects that:
after the micro-interface generator is arranged in the oximation reactor, on one hand, ammonia can be dispersed and crushed into micro-bubbles with the diameter of micron order, and the phase interface area between the ammonia and a liquid phase material is increased, so that the mass transfer space is fully satisfied, the retention time of the ammonia in the liquid phase is increased, and the consumption of the ammonia is reduced, thereby greatly improving the oximation reaction efficiency, effectively inhibiting side reactions and obviously reducing the energy consumption in the reaction process; on the other hand, the reaction temperature and pressure are reduced, the decomposition products of cyclohexanone and cyclohexanone oxime are reduced, the yield and quality of the final product caprolactam are improved, the energy consumption is reduced, and the system safety is improved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic structural diagram of a reaction system for ammoximation and recovery of tert-butanol according to an embodiment of the present invention.
Description of the drawings:
a 10-oximation reactor; 11-tail gas outlet;
12-a discharge hole; 13-an air inlet;
20-reaction clear liquid buffer tank; 30-a tail gas absorption tower;
31-an absorption liquid outlet; a 40-tert-butanol recovery column;
41-liquid inlet; 42-gas inlet;
a 50-tertiary butanol reflux tank; 51-noncondensable gas outlet;
60-a micro-interface generator; 70-full automatic regulation condenser;
80-circulating pump; 90-an outer filtration device;
100-overhead condenser; 110-column kettle reboiler;
120-reflux pump; 130-an exhaust gas cooler;
140-circulation tert-butanol tank.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Examples
Referring to fig. 1, a reaction system for ammoximation and recovery of tert-butanol according to an embodiment of the present invention includes an oximation reactor 10, a reaction clear liquid buffer tank 20, a tail gas absorption tower 30, a tert-butanol recovery tower 40, and a tert-butanol reflux tank 50, wherein a micro interface generator 60 is disposed inside the oximation reactor 10 for dispersing the crushed gas into micro bubbles with a diameter of micron level. Specifically, the side wall of the oximation reactor 10 is provided with an air inlet 13 for introducing raw material ammonia, the air inlet 13 extends into the micro-interface generator 60 through a pipeline, the ammonia is dispersed and broken into micro-bubbles at the micron level in the micro-interface generator 60, and the micro-bubbles are sufficiently emulsified with the liquid phase material in the oximation reactor 10 to perform an ammoximation reaction, so that the mass transfer area between the ammonia and the liquid phase material is effectively increased, the mass transfer resistance is reduced, and the reaction efficiency is improved. In the present embodiment, the micro-interface generator 60 is a pneumatic micro-interface generator, and is driven by ammonia gas. It is understood that the number of the micro-interface generators 60 is not limited in this embodiment, and in order to increase the dispersion and mass transfer effects, additional micro-interface generators may be added, and the micro-interface generators may be arranged inside the oximation reactor in a series or parallel manner or a combination of series and parallel.
Wherein, the ammoximation reaction is a strong exothermic reaction, normal oximation reaction does not need any external heat, the reaction heat energy maintains the heat required in the continuous reaction process, the redundant heat energy causes the temperature rise of materials in the reactor, the temperature in the reaction process is controlled by arranging an external circulation device outside the oximation reactor 10, the external circulation device comprises a circulation pipeline, a full-automatic adjusting condenser 70 is arranged on the circulation pipeline, the full-automatic adjusting condenser 70 can rapidly and automatically cool the circulation materials, in addition, a circulation pump 80 is arranged on the circulation pipeline, in the embodiment, the circulation pump 80 can be vertical or horizontal, the number of pump bodies is unlimited, and one or more of the pump bodies can be installed in series or in parallel to increase the circulation power.
The top of the oximation reactor 10 of this embodiment is provided with a tail gas outlet 11, and the tail gas outlet 11 is connected with a tail gas absorption tower 30, and in the reaction process, unreacted gas enters the tail gas absorption tower 30 from the tail gas outlet 11 for recycling, and in addition, the bottom of the tail gas absorption tower 30 is also provided with an absorption liquid outlet 31, and the absorption liquid outlet 31 is connected with the top of the oximation reactor 10 for the absorption liquid to return to the inside of the reactor for reuse.
The bottom of the oximation reactor 10 is provided with a discharge port 12, the discharge port 12 is connected with a reaction clear liquid buffer tank 20, preferably, an external filtering device 90 can be arranged on a connecting pipeline between the reaction clear liquid buffer tank 20 and the discharge port 12, so that the catalyst is prevented from entering the reaction clear liquid buffer tank 20 after the filter inside the oximation reactor 10 is blocked. The material from the reaction clear liquid buffer tank 20 is introduced from the middle section of the tert-butyl alcohol recovery tower 40 for recovering tert-butyl alcohol, and the top of the tert-butyl alcohol recovery tower 40 is connected with the tert-butyl alcohol reflux tank 50 for gas-liquid separation. Specifically, the middle section of the tert-butyl alcohol recovery tower 40 is respectively provided with a liquid inlet 41 and a gas inlet 42, and the liquid inlet 41 is connected with the bottom of the reaction clear liquid buffer tank 20; the gas inlet 42 is connected with the top of the reaction clear liquid buffer tank 20, and is provided with a gas inlet and a liquid inlet at the same time because the material components in the reaction clear liquid buffer tank are relatively complex, most of the tertiary butanol exists in a liquid state, and a small amount of the tertiary butanol exists in a reaction product in a gaseous state, so that the double-material inlet of the gas inlet and the liquid inlet is arranged, and the tertiary butanol can be fully recycled. In this embodiment, the tert-butyl alcohol recovery tower 40 is a vertical sieve plate tower, which has the characteristics of high utilization rate of mass transfer space and good mass transfer effect, and can effectively solve the problem of high difficulty in separating the tert-butyl alcohol light impurities, and a reasonable reflux ratio and a reasonable feeding position are adopted in the operation to improve the removal efficiency of the tert-butyl alcohol light impurities, more preferably, the bottom end inside the tert-butyl alcohol recovery tower 40 is set into a conical hopper shape, so that only the recovered tert-butyl alcohol can be received, and the cyclohexanone oxime and the tert-butyl alcohol can be better separated by the setting mode, so that the recovery efficiency of the tert-butyl alcohol is improved, and the purity of the tert-butyl alcohol is improved.
A reflux pipeline is arranged between the tertiary butanol recovery tower 40 and the tertiary butanol reflux tank 50, one end of the reflux pipeline is connected with the top of the tertiary butanol recovery tower 40, the other end of the reflux pipeline is connected with the bottom of the tertiary butanol reflux tank 50 to be used for returning substances in the tertiary butanol reflux tank 50 to be continuously separated and purified, a reflux pump 120 is arranged on the reflux pipeline, and a part of condensate is pressurized by the reflux pump 120 and then enters the reflux pipeline to be used as top reflux for absorbing surplus heat at the top of the tertiary butanol recovery tower, so that the heat balance of the whole tower is maintained, and the recovery purity of the tertiary butanol can be improved after multiple times of reflux. Compared with natural reflux, the reflux pump 120 can adjust the reflux amount, so that the reflux amount is stable and the operability is good.
Further, a tower top condenser 100 is arranged at the tower top of the tertiary butanol recovery tower 40, a tower kettle reboiler 110 is arranged at the tower kettle, and substances coming out of the tower top condenser 100 of the tertiary butanol recovery tower 40 firstly flow through the tertiary butanol reflux tank 50 and then return to the tower top.
In order to achieve a better condensation effect, the two tower top condensers 100 are connected in series at the tower top in the embodiment, the first-stage tower top condenser adopts circulating cooling water for condensation, and the second-stage tower top condenser adopts frozen brine for condensation. More preferably, in order to avoid the hydrolysis of cyclohexanone oxime into cyclohexanone at high temperature, the tower reboiler 110 employs a once-through thermosiphon reboiler to reduce the high-temperature retention time of oxime water.
In addition, a vent gas cooler 130 is arranged on a pipeline connecting the tail gas outlet 11 and the tail gas absorption tower 30, the tertiary butanol reflux tank 50 is provided with a non-condensable gas outlet 51, and the non-condensable gas outlet 51 is connected with the vent gas cooler 130, so that the non-condensable gas and the tail gas are mixed and then enter the tail gas absorption tower 30 for recycling.
In this embodiment, the reaction system further includes a circulating tert-butanol tank 140, the top of the circulating tert-butanol tank 140 is connected to the bottom of the tert-butanol reflux tank 50, and the bottom of the circulating tert-butanol tank 140 is connected to the bottom of the oximation reactor 10, so that tert-butanol can be reused as a reaction solvent. A small part of condensate in the tertiary butanol reflux tank 50 is used as tower top reflux, and the rest of condensate enters the oximation reactor 10 through the circulating tertiary butanol tank 140 to be reused as reaction solvent, so that the use cost of the tertiary butanol is reduced. More preferably, the circulating tertiary butanol tank 140 may be provided with an automatic spray of condensed water so that the temperature inside the tank may be kept constant.
The operation and principle of the reaction system for ammoximation and recovery of t-butanol according to the present invention will be briefly described below.
Ammonia gas firstly enters the micro-interface generator 60 through the gas inlet 13 to be dispersed and crushed into micro-bubbles at the micron level, meanwhile, liquid-phase mixed raw materials (including hydrogen peroxide, cyclohexanone, circulating tert-butyl alcohol, circulating materials and the like) enter the oximation reactor 10, and the dispersed and crushed micro-bubbles and the liquid-phase mixed raw materials are fully emulsified, so that the mass transfer area of a gas phase and a liquid phase is effectively increased, and the mass transfer resistance is reduced.
The emulsion after being emulsified fully undergoes oximation reaction in the oximation reactor 10 under the action of the catalyst, the temperature in the oximation reactor 10 is 80-82 ℃, and the pressure is 0.18-0.23 MPa. Wherein, the ammoximation reaction is a strong exothermic reaction, and the circulating material is rapidly and automatically cooled through the full-automatic adjusting condenser 70 arranged on the outer circulating pipeline, so that the temperature in the reactor is reduced.
In the reaction process, unreacted ammonia, alcohol and other gases enter the tail gas absorption tower 30 after being cooled by the exhaust gas cooler 130 from the tail gas outlet 11, the tail gas absorption tower 30 absorbs the ammonia and the alcohol in the gases into absorption liquid by using desalted water, and the absorption liquid enters the oximation reactor 10 for repeated recycling after coming out from the absorption liquid outlet 31. The oximation reaction products (cyclohexanone oxime, ammonia, a small amount of tertiary butanol and the like) enter a reaction clear liquid buffer tank 20 through a discharge hole 12 in a clear liquid mode, then enter the tower through a liquid inlet 41 and a gas inlet 42 of a tertiary butanol recovery tower 40 respectively for recovering the tertiary butanol, mixed distillate containing water, ammonia and the tertiary butanol, which is distilled from the top of the tertiary butanol recovery tower 40, enters a tertiary butanol reflux tank 50 after being cooled by a tower top condenser 100, and uncondensed gas enters a tail gas absorption tower 30 for recovering ammonia after being mixed with tail gas of an oximation reactor 10 through an uncondensed gas outlet 51 through a discharge gas cooler 130. A small part of the condensate in the tertiary butanol reflux tank 50 is pressurized by the reflux pump 120 and then used as tower top reflux, and the rest of the condensate enters the oximation reactor 10 through the circulating tertiary butanol tank 140 and is reused as a reaction solvent, so that the use cost of the tertiary butanol is reduced.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A reaction system for ammoximation and recovery of tert-butyl alcohol is characterized by comprising an oximation reactor, a reaction clear liquid buffer tank, a tail gas absorption tower, a tert-butyl alcohol recovery tower and a tert-butyl alcohol reflux tank, wherein,
a tail gas outlet is formed in the top of the oximation reactor, a discharge hole is formed in the bottom of the oximation reactor, the discharge hole is connected with the reaction clear liquid buffer tank, the tail gas outlet is connected with the tail gas absorption tower, materials from the reaction clear liquid buffer tank are introduced from the middle section of the tert-butyl alcohol recovery tower to be used for recovering tert-butyl alcohol, and the top of the tert-butyl alcohol recovery tower is connected with the tert-butyl alcohol reflux tank to be used for gas-liquid separation;
an external circulation heat exchange device is arranged outside the oximation reactor and is used for controlling the temperature inside the oximation reactor; the interior of the oximation reactor is provided with a micro-interface generator which is used for dispersing the broken gas into micro-bubbles with the diameter of micron level.
2. The reaction system for ammoximation and recovery of tert-butanol according to claim 1, wherein the side wall of the oximation reactor is provided with an air inlet for introducing raw ammonia gas, the air inlet extends to the inside of the micro-interface generator through a pipeline, the type of the micro-interface generator is a pneumatic micro-interface generator, the number of the micro-interface generators is more than one, and each micro-interface generator is connected in parallel.
3. The reaction system for ammoximation and recovery of tert-butanol according to claim 1, wherein a liquid inlet and a gas inlet are respectively arranged at the middle section of the tert-butanol recovery tower, and the liquid inlet is connected with the bottom of the reaction clear liquid buffer tank; the gas inlet is connected with the top of the reaction clear liquid buffer tank.
4. The reaction system for ammoximation and recovery of tertiary butanol according to claim 1, wherein the top of the tertiary butanol recovery tower is provided with an overhead condenser, and the bottom of the tower is provided with a bottom reboiler.
5. The reaction system for ammoximation and recovery of tert-butanol according to claim 1, further comprising a return line, wherein one end of the return line is connected with the top of the tert-butanol recovery column, and the other end of the return line is connected with the bottom of the tert-butanol return tank for returning the substances in the tert-butanol return tank to continue separation and purification; and a reflux pump is arranged on the reflux pipeline.
6. The reaction system for ammoximation and recovery of tert-butanol according to claim 1, wherein a pipeline connecting the tail gas outlet and the tail gas absorption tower is provided with an exhaust gas cooler, the tert-butanol reflux tank is provided with a non-condensable gas outlet, and the non-condensable gas outlet is connected with the exhaust gas cooler so that the non-condensable gas and the tail gas are mixed and then enter the tail gas absorption tower for recycling.
7. The ammoximation and tertiary butanol recovery reaction system of any one of claims 1-6, wherein the tertiary butanol recovery column is of the type of a vertical sieve plate column.
8. The ammoximation and tert-butanol recovery reaction system according to any one of claims 1 to 6, wherein the reaction system further comprises a circulating tert-butanol tank, the top of the circulating tert-butanol tank is connected with the bottom of the tert-butanol reflux tank, and the bottom of the circulating tert-butanol tank is connected with the bottom of the oximation reactor, so that tert-butanol can be reused as a reaction solvent.
9. The method for ammoximation and recovery of tert-butanol using the reaction system for ammoximation and recovery of tert-butanol according to any one of claims 1 to 8, comprising the steps of:
after ammonia gas is dispersed and crushed into micro bubbles, the micro bubbles and liquid-phase materials are subjected to catalytic oximation reaction; in the process of carrying out the catalytic oximation reaction, the gas which is not completely reacted is recycled, and the tertiary butanol in the reaction product is recycled after the reaction product is collected in a clear liquid manner.
10. The process of claim 9, wherein the temperature of the oximation reaction is 80-82 ℃ and the pressure is 0.18-0.23 MPa.
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| CN202010284848.7A CN111574399A (en) | 2020-04-13 | 2020-04-13 | Reaction system and method for ammoximation and recovery of tert-butyl alcohol |
| PCT/CN2020/092774 WO2021208199A1 (en) | 2020-04-13 | 2020-05-28 | Reaction system and method for ammoximation and tert-butyl alcohol recovery |
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| CN113121314A (en) * | 2021-05-17 | 2021-07-16 | 吴嘉 | Device and method for recycling tertiary butanol by using dividing wall rectifying tower and combining heat pump technology |
| CN113477205A (en) * | 2021-07-14 | 2021-10-08 | 南京延长反应技术研究院有限公司 | Automatic gas-liquid mixing system and method thereof |
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| CN116036626B (en) * | 2022-11-22 | 2023-09-29 | 安徽海华科技集团有限公司 | Quick high-efficient dewatering system of reaction raw materials |
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