CN113121313A - Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent - Google Patents
Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent Download PDFInfo
- Publication number
- CN113121313A CN113121313A CN202110534471.0A CN202110534471A CN113121313A CN 113121313 A CN113121313 A CN 113121313A CN 202110534471 A CN202110534471 A CN 202110534471A CN 113121313 A CN113121313 A CN 113121313A
- Authority
- CN
- China
- Prior art keywords
- rectifying tower
- tower
- reboiler
- rectifying
- condenser
- 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.)
- Pending
Links
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000011084 recovery Methods 0.000 title claims abstract description 33
- 239000007810 chemical reaction solvent Substances 0.000 title claims abstract description 26
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 45
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000498 cooling water Substances 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229940127218 antiplatelet drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000000106 platelet aggregation inhibitor Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- 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
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/52—Heat recovery pumps, i.e. heat pump based systems or units able to transfer the thermal energy from one area of the premises or part of the facilities to a different one, improving the overall efficiency
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to an energy-saving recovery device and method for tert-butyl alcohol serving as an ammoximation reaction solvent, and belongs to the technical field of chemical separation. The device disclosed by the invention comprises a rectifying tower I, a rectifying tower I condenser, a rectifying tower I tower bottom reboiler, a rectifying tower II, a compressor and a rectifying tower II tower bottom reboiler; the method for energy-saving recovery of the ammoximation reaction solvent tert-butyl alcohol by using the device can greatly reduce steam consumption and cooling water consumption, has good energy-saving effect, has strong separation capability on impurities, and avoids influence on the subsequent cyclohexanone oxime refining process because the content of the tert-butyl alcohol in the obtained cyclohexanone oxime aqueous solution is very low.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and particularly relates to an energy-saving recovery device and an energy-saving recovery method for ammoximation reaction solvent tert-butyl alcohol.
Background
Caprolactam is an important organic chemical raw material, is mainly used for synthesizing polyamide (commonly called nylon, abbreviated as PA), producing PA6 fiber (namely chinlon), PA6 engineering plastics, films and the like, can also be used for producing antiplatelet drugs, 6-aminocaproic acid and the like, and has wide application. The ammoximation reaction is an important step in the production of caprolactam.
The ammoximation reaction takes cyclohexanone, hydrogen peroxide and liquid ammonia as raw materials, tert-butyl alcohol as a solvent, and cyclohexanone oxime is generated by reaction under the action of a catalyst and is used as a raw material for rearrangement refining of caprolactam. Tert-butanol serves as a solvent, does not participate in the reaction, and needs to be recovered and recycled in order to improve the utilization rate of the tert-butanol.
The tertiary butanol recovery usually adopts a conventional single-tower rectification process, and adopts a rectification tower to realize the separation of the tertiary butanol and water: ammonia gas and tert-butyl alcohol aqueous solution are extracted from the tower top, and condensation of tert-butyl alcohol vapor is realized by an air cooler, so that a large amount of electric energy and circulating cooling water are consumed; cyclohexanone oxime aqueous solution is extracted from the tower bottom, and the reboiler is heated by raw steam, so that the steam consumption is high. Although the tertiary butanol single-tower rectification process has many years of engineering practical application and mature and reliable technology, the tertiary butanol single-tower rectification process has the defects of old technology and high energy consumption cost. In order to reduce the process energy consumption, a double-tower double-effect rectification process is provided, steam at the top of a first-effect rectification tower is used as a heat source of a reboiler at the bottom of a second-effect rectification tower, such as patents ZL201210079947.7 and ZL201510372543.0, the steam consumption can be reduced by more than 40% compared with that of a single-tower rectification process, the energy-saving effect is obvious, but the reboiler at the bottom of the first-effect rectification tower still needs to be heated by external raw steam, and the steam consumption is still large; meanwhile, the overhead steam of the double-effect rectifying tower still needs to be condensed by using a large amount of circulating cooling water, so that the total energy cost of the rectifying process is still high. In addition, one rectifying tower in the double-effect rectifying process is operated under pressure so as to obtain high-temperature materials to maintain the heat transfer temperature difference required by latent heat utilization, but when the temperature is higher, cyclohexanone oxime is easy to hydrolyze, and the yield of the product is influenced.
Therefore, in order to further reduce the energy cost and prevent the hydrolysis of cyclohexanone oxime at high temperature, further improvement and research on the device for recovering tertiary butanol as an ammoximation reaction solvent in energy conservation are needed, and a new device and a method for recovering energy conservation are provided.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an energy-saving recovery apparatus for t-butanol as a solvent in an ammoximation reaction using an open heat pump; the invention also aims to provide an energy-saving recovery device for the solvent tert-butyl alcohol of the ammoximation reaction by using a closed heat pump; the invention also aims to provide a method for the energy-saving recovery of tert-butyl alcohol which is an ammoximation reaction solvent of an open heat pump; the invention also aims to provide a method for recovering tert-butyl alcohol from an ammoximation reaction solvent by using a closed heat pump in an energy-saving manner.
1. The energy-saving recovery device for the ammoximation reaction solvent tert-butyl alcohol by using the open heat pump comprises a rectifying tower I2, a rectifying tower I condenser 3, a rectifying tower I tower bottom reboiler 4, a rectifying tower II 5, a compressor 6 and a rectifying tower II tower bottom reboiler 7;
the top of the rectifying tower I2 is connected with a rectifying tower I condenser 3, the bottom of the rectifying tower I2 is connected with a cold side inlet of a rectifying tower I bottom reboiler 4, and a cold side outlet of the rectifying tower I bottom reboiler 4 is connected with the lower part of a rectifying tower I2; the bottom of the rectifying tower I2 is connected with the feed inlet of a rectifying tower II 5;
the top of rectifying column II 5 links to each other with compressor 6, the hot side entry of II tower bottoms reboiler 7 of rectifying column in proper order, the hot side export of II tower bottoms reboiler 7 of rectifying column links to each other with the upper portion of II 5 of rectifying column, the tower bottom of II tower bottoms reboiler 7 of rectifying column links to each other with II tower bottoms reboiler 7 of rectifying column's cold side entry at the tower bottom of rectifying column, II tower bottoms reboiler 7 of rectifying column's cold side export links to each other with II 5 lower part of rectifying column.
Preferably, the device is also provided with a preheater 1, and the preheater 1 is connected with the feed inlet of the rectifying tower I2.
2. The energy-saving recovery method of the ammoximation reaction solvent tert-butyl alcohol by using the open heat pump adopts the energy-saving recovery device of the ammoximation reaction solvent tert-butyl alcohol by using the open heat pump for recovery, and specifically comprises the following steps:
a. the preheated ammoximation reaction product enters a rectifying tower I2 for rectification treatment, mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I2 and enters a rectifying tower I condenser 3, part of liquid phase components generated after condensation are returned to the rectifying tower I2 from the top of the tower as reflux liquid, and the other part of the liquid phase components are recovered as a recovered solvent I;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I2, one part of the mixed liquid enters the cold side of a reboiler 4 at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I2 after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II 5;
b. the bottom material of the rectifying tower I2 enters a rectifying tower II 5 for rectification treatment, mixed steam II containing tert-butyl alcohol, water and ammonia is obtained at the top of the rectifying tower II 5, enters a compressor 6 for pressurization to improve the energy grade and then enters the hot side of a reboiler 7 at the bottom of the rectifying tower II to provide a heat source for the reboiler 7 at the bottom of the rectifying tower II and simultaneously carry out heat exchange and condensation to obtain a recovered solvent II, one part of the recovered solvent II is taken as a reflux liquid and returns to the rectifying tower II 5 from the top of the tower, and the other part of the recovered solvent II is taken out and returned to an ammoximation process together with the recovered solvent I for recycling;
and (3) obtaining the cyclohexanone-oxime aqueous solution at the bottom of the rectifying tower II 5, allowing one part of the cyclohexanone-oxime aqueous solution to enter the cold side of a reboiler 7 at the bottom of the rectifying tower II, returning the cyclohexanone-oxime aqueous solution to the rectifying tower II 5 after heat exchange, and extracting the other part of the cyclohexanone-oxime aqueous solution to be sent to a subsequent working procedure.
Preferably, the preheated ammoximation reaction product is preheated by taking any one or more of a recovered solvent II, an extracted cyclohexanone oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange at the hot side of a reboiler 4 at the bottom of the rectifying tower I as a heat source.
Further preferably, the reboiler 4 at the bottom of the rectifying tower I is heated by raw steam.
3. The energy-saving recovery device for the ammoximation reaction solvent tert-butyl alcohol by using the closed heat pump comprises a rectifying tower I2, a rectifying tower I condenser 3, a rectifying tower I tower bottom reboiler 4, a rectifying tower II 5, a compressor 6, a rectifying tower II tower bottom reboiler 7 and a rectifying tower II condenser 8;
the top of the rectifying tower I2 is connected with a rectifying tower I condenser 3, the bottom of the rectifying tower I2 is connected with a cold side inlet of a rectifying tower I bottom reboiler 4, and a cold side outlet of the rectifying tower I bottom reboiler 4 is connected with the lower part of a rectifying tower I2; the bottom of the rectifying tower I2 is connected with the feed inlet of a rectifying tower II 5;
the top of the rectifying tower II 5 is connected with a hot side inlet of a rectifying tower II condenser 8, and a hot side outlet of the rectifying tower II condenser 8 is connected with the upper part of the rectifying tower II 5; the tower bottom of the rectifying tower II 5 is connected with a cold side inlet of a reboiler 7 at the tower bottom of the rectifying tower II, and a cold side outlet of the reboiler 7 at the tower bottom of the rectifying tower II is connected with the lower part of the rectifying tower II 5;
and a cold side outlet of the condenser 8 of the rectifying tower II is sequentially connected with the compressor 6 and a hot side inlet of the reboiler 7 at the bottom of the rectifying tower II, and a hot side outlet of the reboiler 7 at the bottom of the rectifying tower II is connected with a cold side inlet of the condenser 8 of the rectifying tower II to form heat pump circulation.
Preferably, the device is also provided with a preheater 1, and the preheater 1 is connected with the feed inlet of the rectifying tower I2.
4. The energy-saving recovery method of the ammoximation reaction solvent tert-butyl alcohol by using the closed heat pump adopts the energy-saving recovery device of the ammoximation reaction solvent tert-butyl alcohol by using the closed heat pump for recovery, and specifically comprises the following steps:
a. the preheated ammoximation reaction product enters a rectifying tower I2 for rectification treatment, mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I2 and enters a rectifying tower I condenser 3, part of liquid phase components generated after condensation are returned to the rectifying tower I2 from the top of the tower as reflux liquid, and the other part of the liquid phase components are recovered as a recovered solvent I;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I2, one part of the mixed liquid enters the cold side of a reboiler 4 at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I2 after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II 5;
b. discharging from the bottom of the rectifying tower I2, feeding the discharged material into a rectifying tower II 5 for rectification treatment, obtaining mixed steam II containing tert-butyl alcohol, water and ammonia at the top of the rectifying tower II 5, feeding the mixed steam II into the hot side of a condenser 8 of the rectifying tower II, condensing to obtain a recovered solvent II, returning one part of the recovered solvent II as a reflux liquid to the rectifying tower II 5 from the top of the rectifying tower, collecting the other part of the recovered solvent II, and returning the recovered solvent II and the recovered solvent I to an ammoximation process for recycling;
heat pump working medium liquid on the cold side of a condenser 8 of a rectifying tower II exchanges heat with mixed steam II to generate heat pump working medium steam, the heat pump working medium steam is pressurized by a compressor 6 to improve the energy grade and then enters the hot side of a reboiler 7 at the bottom of the rectifying tower II to provide a heat source for the reboiler 7 at the bottom of the rectifying tower II and exchange heat and condense to obtain heat pump working medium liquid, and the heat pump working medium liquid returns to the cold side of the condenser 8 of the rectifying tower II to form heat pump circulation;
and (3) obtaining the cyclohexanone-oxime aqueous solution at the bottom of the rectifying tower II 5, allowing one part of the cyclohexanone-oxime aqueous solution to enter the cold side of a reboiler 7 at the bottom of the rectifying tower II, returning the cyclohexanone-oxime aqueous solution to the rectifying tower II 5 after heat exchange, and extracting the other part of the cyclohexanone-oxime aqueous solution to be sent to a subsequent working procedure.
Preferably, the preheated ammoximation reaction product is preheated by taking any one or more of a recovered solvent II, an extracted cyclohexanone oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange at the hot side of a reboiler 4 at the bottom of the rectifying tower I as a heat source.
Further preferably, the reboiler 4 at the bottom of the rectifying tower I is heated by raw steam.
The invention has the beneficial effects that:
1. the invention discloses an energy-saving recovery device and a method for tert-butyl alcohol serving as an ammoximation reaction solvent, wherein a heat pump is adopted for rectification in the device, low-grade heat energy at the top of a rectifying tower is converted into high-grade heat energy, and condensation heat of materials at the top of the rectifying tower is utilized to supply heat to a reboiler at the bottom of the rectifying tower, so that the latent heat of vaporization is recycled, the consumption of generated steam and circulating cooling water is reduced, meanwhile, heat integration is designed, the heat in the system is used as a heat source of a preheater, and the process energy consumption is further reduced;
2. in the device and the method disclosed by the invention, the rectifying tower is operated under the normal pressure condition, the system temperature can be controlled at a lower level, and the cyclohexanone-oxime is prevented from being hydrolyzed to influence the yield of the product;
3. the device and the method disclosed by the invention have stronger separation capability on impurities, the content of the tertiary butanol in the obtained cyclohexanone oxime aqueous solution is very low, and the influence on the subsequent cyclohexanone oxime refining process is avoided.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is an energy-saving recovery apparatus of t-butanol as a solvent for ammoximation reaction using an open heat pump in example 1;
FIG. 2 is an energy-saving recovery device of a tertiary butanol as an ammoximation reaction solvent in example 2, wherein a closed heat pump is used;
wherein 1 is a preheater, 2 is a rectifying tower I, 3 is a rectifying tower I condenser, 4 is a rectifying tower I tower bottom reboiler, 5 is a rectifying tower II, 6 is a compressor, and 7 is a rectifying tower II tower bottom reboiler; and 8 is a condenser of the rectifying tower II.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that, in the following embodiments, features in the embodiments may be combined with each other without conflict.
Example 1
1. An energy-saving recovery device for ammoximation reaction solvent tert-butyl alcohol by using an open heat pump is shown in figure 1 and comprises a rectifying tower I2, a rectifying tower I condenser 3, a rectifying tower I tower bottom reboiler 4, a rectifying tower II 5, a compressor 6 and a rectifying tower II tower bottom reboiler 7;
the top of the rectifying tower I2 is connected with a rectifying tower I condenser 3, the bottom of the rectifying tower I2 is connected with a cold side inlet of a rectifying tower I bottom reboiler 4, and a cold side outlet of the rectifying tower I bottom reboiler 4 is connected with the lower part of a rectifying tower I2; the bottom of the rectifying tower I2 is connected with the feed inlet of a rectifying tower II 5;
the top of the rectifying tower II 5 is sequentially connected with a compressor 6 and a hot side inlet of a reboiler 7 at the bottom of the rectifying tower II, a hot side outlet of the reboiler 7 at the bottom of the rectifying tower II is connected with the upper part of the rectifying tower II 5, the bottom of the rectifying tower II 5 is connected with a cold side inlet of the reboiler 7 at the bottom of the rectifying tower II, and a cold side outlet of the reboiler 7 at the bottom of the rectifying tower II is connected with the lower part of the rectifying tower II 5.
The device is also provided with a preheater 1, and the preheater 1 is connected with the feed inlet of the rectifying tower I2.
2. The device is adopted for carrying out the energy-saving recovery of the ammoximation reaction solvent tert-butyl alcohol, and the method specifically comprises the following steps:
a. the ammoximation reaction product preheated by the preheater 1 (any one or more of a recovered solvent II, a produced cyclohexanone oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange of a hot side of a reboiler 4 at the bottom of a rectifying tower I is used as a heat source in the preheating process) enters a rectifying tower I2 for rectification treatment, the mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I2 and enters a rectifying tower I condenser 3, part of liquid phase components generated after condensation is used as reflux liquid and returns to the rectifying tower I2 from the top of the rectifying tower, and the part of liquid phase components is recovered as the recovered solvent I, and uncondensed vapor phase components are a mixture of the light components and the ammonia and are sent to a tail gas treatment system;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I2, one part of the mixed liquid enters the cold side of a reboiler 4 at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I2 after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II 5;
b. the bottom material of the rectifying tower I2 enters a rectifying tower II 5 for rectification treatment, mixed steam II containing tert-butyl alcohol, water and ammonia is obtained at the top of the rectifying tower II 5, enters a compressor 6 for pressurization and energy grade improvement, enters the hot side of a reboiler 7 at the bottom of the rectifying tower II, provides a heat source for the reboiler 7 at the bottom of the rectifying tower II and simultaneously exchanges heat and condenses to obtain a recovered solvent II, one part of the recovered solvent II is used as a reflux liquid and returns to the rectifying tower II 5 from the top of the tower, and the other part of the recovered solvent II is returned to an ammoximation process together with the recovered solvent I for recycling;
and (3) obtaining the cyclohexanone-oxime aqueous solution at the bottom of the rectifying tower II 5, allowing one part of the cyclohexanone-oxime aqueous solution to enter the cold side of a reboiler 7 at the bottom of the rectifying tower II, returning the cyclohexanone-oxime aqueous solution to the rectifying tower II 5 after heat exchange, and extracting the other part of the cyclohexanone-oxime aqueous solution to be sent to a subsequent working procedure.
And a reboiler 4 at the bottom of the rectifying tower I adopts raw steam for heating.
In this example, the ammonia content in the recovered solvent I was higher than that in the recovered solvent ii. The rectifying tower I is operated under normal pressure, the operating temperature is 60-90 ℃, and the reflux ratio at the top of the tower is selected within the range of 0.2-3. The rectifying tower II is operated under normal pressure, the operating temperature is 70-120 ℃, and the reflux ratio at the top of the tower is selected within the range of 0.3-5. Compared with the traditional single-tower rectification process, the energy can be saved by 61.1 percent, and compared with the double-tower double-effect rectification process, the energy can be saved by 26.8 percent.
Example 2
1. An energy-saving recovery device for an ammoximation reaction solvent tert-butyl alcohol by using a closed heat pump is shown in figure 2 and comprises a rectifying tower I2, a rectifying tower I condenser 3, a rectifying tower I tower bottom reboiler 4, a rectifying tower II 5, a compressor 6, a rectifying tower II tower bottom reboiler 7 and a rectifying tower II condenser 8;
the top of the rectifying tower I2 is connected with a rectifying tower I condenser 3, the bottom of the rectifying tower I2 is connected with a cold side inlet of a rectifying tower I bottom reboiler 4, and a cold side outlet of the rectifying tower I bottom reboiler 4 is connected with the lower part of a rectifying tower I2; the bottom of the rectifying tower I2 is connected with the feed inlet of a rectifying tower II 5;
the top of the rectifying tower II 5 is connected with a hot side inlet of a rectifying tower II condenser 8, and a hot side outlet of the rectifying tower II condenser 8 is connected with the upper part of the rectifying tower II 5; the tower bottom of the rectifying tower II 5 is connected with a cold side inlet of a reboiler 7 at the tower bottom of the rectifying tower II, and a cold side outlet of the reboiler 7 at the tower bottom of the rectifying tower II is connected with the lower part of the rectifying tower II 5;
and a cold side outlet of the condenser 8 of the rectifying tower II is sequentially connected with the compressor 6 and a hot side inlet of the reboiler 7 at the bottom of the rectifying tower II, and a hot side outlet of the reboiler 7 at the bottom of the rectifying tower II is connected with a cold side inlet of the condenser 8 of the rectifying tower II to form heat pump circulation.
In addition, a preheater 1 is also arranged in the device, and the preheater 1 is connected with the feed inlet of the rectifying tower I2.
2. The device is adopted to carry out the energy-saving recovery of the ammoximation reaction solvent tert-butyl alcohol, and the method specifically comprises the following steps:
a. the ammoximation reaction product preheated by the preheater 1 enters a rectifying tower I2 for rectification treatment, mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I2 and enters a rectifying tower I condenser 3, part of liquid phase components generated after condensation are returned to the rectifying tower I2 as reflux liquid from the top of the tower, part of the liquid phase components are collected as a recovered solvent I, and uncondensed vapor phase components are a mixture of the light components and ammonia and are sent to a tail gas treatment system;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I2, one part of the mixed liquid enters the cold side of a reboiler 4 at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I2 after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II 5;
b. discharging from the bottom of the rectifying tower I2, feeding the discharged material into a rectifying tower II 5 for rectification treatment, obtaining mixed steam II containing tert-butyl alcohol, water and ammonia at the top of the rectifying tower II 5, feeding the mixed steam II into the hot side of a condenser 8 of the rectifying tower II, condensing to obtain a recovered solvent II, returning one part of the recovered solvent II as a reflux liquid to the rectifying tower II 5 from the top of the rectifying tower, and collecting the other part of the recovered solvent II, and returning the recovered solvent II and the recovered solvent I to an ammoximation process for recycling;
heat pump working medium liquid on the cold side of a condenser 8 of a rectifying tower II exchanges heat with mixed steam II to generate heat pump working medium steam, the heat pump working medium steam is pressurized by a compressor 6 to improve the energy grade and then enters the hot side of a reboiler 7 at the bottom of the rectifying tower II to provide a heat source for the reboiler 7 at the bottom of the rectifying tower II and exchange heat and condense to obtain heat pump working medium liquid, and the heat pump working medium liquid returns to the cold side of the condenser 8 of the rectifying tower II to form heat pump circulation;
and (3) obtaining the cyclohexanone-oxime aqueous solution at the bottom of the rectifying tower II 5, allowing one part of the cyclohexanone-oxime aqueous solution to enter the cold side of a reboiler 7 at the bottom of the rectifying tower II, returning the cyclohexanone-oxime aqueous solution to the rectifying tower II 5 after heat exchange, and extracting the other part of the cyclohexanone-oxime aqueous solution to be sent to a subsequent working procedure.
Wherein the preheater 1 takes any one or more of a recovered solvent II, an extracted cyclohexanone-oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange of a hot side of a reboiler 4 at the bottom of a rectifying tower I as a heat source.
Meanwhile, a reboiler 4 at the bottom of the rectifying tower I adopts raw steam for heating.
In this example, the ammonia content in the recovered solvent I was higher than that in the recovered solvent ii. The rectifying tower I is operated under normal pressure, the operating temperature is 60-90 ℃, and the reflux ratio at the top of the tower is selected within the range of 0.2-3. The rectifying tower II is operated under normal pressure, the operating temperature is 70-120 ℃, and the reflux ratio at the top of the tower is selected within the range of 0.3-5. Compared with the traditional single-tower double-effect rectification process, the energy can be saved by 58.4 percent, and compared with the double-tower double-effect rectification process, the energy can be saved by 21.8 percent.
In conclusion, the invention discloses an energy-saving recovery device and method for tert-butyl alcohol as an ammoximation reaction solvent, wherein the device adopts heat pump rectification to convert low-grade heat energy at the top of a rectifying tower into high-grade heat energy, and supplies heat to a reboiler at the bottom of the tower by using condensation heat of materials at the top of the tower, so that the recycling of latent heat of vaporization is realized, the consumption of generated steam and circulating cooling water is reduced, meanwhile, heat integration is designed, the heat in a system is used as a heat source of a preheater, and the process energy consumption is further reduced, compared with the traditional single-tower rectification process, the energy can be saved by more than 55%, and compared with a double-tower double-effect rectification process, the energy can; meanwhile, the rectifying tower in the device disclosed by the invention is operated under the normal pressure condition, the system temperature can be controlled at a lower level, and the cyclohexanone-oxime is prevented from being hydrolyzed to influence the yield of the product. The energy-saving recovery method of the ammoximation reaction solvent tert-butyl alcohol disclosed by the invention has stronger separation capability on impurities, and the obtained cyclohexanone oxime aqueous solution has very low content of tert-butyl alcohol, thereby avoiding influencing the subsequent cyclohexanone oxime refining process.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The energy-saving recovery device for the ammoximation reaction solvent tert-butyl alcohol by using the open heat pump is characterized by comprising a rectifying tower I (2), a rectifying tower I condenser (3), a rectifying tower I tower bottom reboiler (4), a rectifying tower II (5), a compressor (6) and a rectifying tower II tower bottom reboiler (7);
the top of the rectifying tower I (2) is connected with a rectifying tower I condenser (3), the bottom of the rectifying tower I (2) is connected with a cold side inlet of a rectifying tower I bottom reboiler (4), and a cold side outlet of the rectifying tower I bottom reboiler (4) is connected with the lower part of the rectifying tower I (2); the tower bottom of the rectifying tower I (2) is connected with the feed inlet of the rectifying tower II (5);
the top of rectifying column II (5) links to each other with compressor (6), the hot side entry of rectifying column II tower bottom reboiler (7) in proper order, the hot side export of rectifying column II tower bottom reboiler (7) links to each other with the upper portion of rectifying column II (5), the tower bottom of rectifying column II (5) links to each other with the cold side entry of rectifying column II tower bottom reboiler (7), the cold side export of rectifying column II tower bottom reboiler (7) links to each other with the lower part of rectifying column II (5).
2. The apparatus according to claim 1, characterized in that the apparatus further comprises a preheater (1), the preheater (1) being connected to the feed inlet of the rectification column I (2).
3. The energy-saving recovery device for the ammoximation reaction solvent tert-butyl alcohol by using the closed heat pump is characterized by comprising a rectifying tower I (2), a rectifying tower I condenser (3), a rectifying tower I tower bottom reboiler (4), a rectifying tower II (5), a compressor (6), a rectifying tower II tower bottom reboiler (7) and a rectifying tower II condenser (8);
the top of the rectifying tower I (2) is connected with a rectifying tower I condenser (3), the bottom of the rectifying tower I (2) is connected with a cold side inlet of a rectifying tower I bottom reboiler (4), and a cold side outlet of the rectifying tower I bottom reboiler (4) is connected with the lower part of the rectifying tower I (2); the tower bottom of the rectifying tower I (2) is connected with the feed inlet of the rectifying tower II (5);
the tower top of the rectifying tower II (5) is connected with a hot side inlet of a rectifying tower II condenser (8), and a hot side outlet of the rectifying tower II condenser (8) is connected with the upper part of the rectifying tower II (5); the tower bottom of the rectifying tower II (5) is connected with a cold side inlet of a reboiler (7) at the tower bottom of the rectifying tower II, and a cold side outlet of the reboiler (7) at the tower bottom of the rectifying tower II is connected with the lower part of the rectifying tower II (5);
and a cold side outlet of the condenser (8) of the rectifying tower II is sequentially connected with a hot side inlet of the reboiler (7) at the bottom of the compressor (6) and the rectifying tower II, and a hot side outlet of the reboiler (7) at the bottom of the rectifying tower II is connected with a cold side inlet of the condenser (8) of the rectifying tower II to form a heat pump circulation.
4. The apparatus according to claim 3, characterized in that the apparatus further comprises a preheater (1), the preheater (1) being connected to the feed inlet of the rectification column I (2).
5. The method for the energy-saving recovery of tert-butyl alcohol serving as an ammoximation reaction solvent of an open heat pump is characterized by adopting the device of claim 1 for recovery, and specifically comprises the following steps:
a. the preheated ammoximation reaction product enters a rectifying tower I (2) for rectification treatment, mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I (2) and enters a rectifying tower I condenser (3), part of liquid phase components generated after condensation are returned to the rectifying tower I (2) from the top of the tower as reflux liquid, part of the liquid phase components are extracted as a recovered solvent I, and uncondensed vapor phase components are a mixture of the light components and ammonia and are sent to a tail gas treatment system;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I (2), one part of the mixed liquid enters the cold side of a reboiler (4) at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I (2) after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II (5);
b. the method comprises the following steps that (1) the discharged material at the bottom of a rectifying tower I (2) enters a rectifying tower II (5) for rectification treatment, mixed steam II containing tert-butyl alcohol, water and ammonia is obtained at the top of the rectifying tower II (5), enters a compressor (6) for pressurization and energy grade improvement, enters the hot side of a reboiler (7) at the bottom of the rectifying tower II to provide a heat source for the reboiler (7) at the bottom of the rectifying tower II and perform heat exchange and condensation to obtain a recovered solvent II, one part of the recovered solvent II is returned to the rectifying tower II (5) from the top of the rectifying tower as a reflux liquid, and the other part of the recovered solvent II is returned to an ammoximation process together with the recovered solvent;
and (3) obtaining cyclohexanone oxime aqueous solution at the bottom of the rectifying tower II (5), allowing one part of the cyclohexanone oxime aqueous solution to enter the cold side of a reboiler (7) at the bottom of the rectifying tower II, returning the cyclohexanone oxime aqueous solution to the rectifying tower II (5) after heat exchange, and extracting the other part of the cyclohexanone oxime aqueous solution to be sent to a subsequent process.
6. The method according to claim 5, wherein the preheated ammoximation reaction product is preheated by taking any one or more of recovered solvent II, extracted cyclohexanone oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange of a hot side of a reboiler (4) at the bottom of the rectifying tower I.
7. The method according to claim 6, characterized in that the rectifying tower I bottom reboiler (4) is heated with raw steam.
8. The method for the energy-saving recovery of tert-butyl alcohol serving as an ammoximation reaction solvent by using a closed heat pump is characterized by adopting the device of claim 3 for recovery, and specifically comprises the following steps:
a. the preheated ammoximation reaction product enters a rectifying tower I (2) for rectification treatment, mixed steam I containing water, tert-butyl alcohol, ammonia and other light components is obtained at the top of the rectifying tower I (2) and enters a rectifying tower I condenser (3), part of liquid phase components generated after condensation are returned to the rectifying tower I (2) from the top of the tower as reflux liquid, part of the liquid phase components are extracted as a recovered solvent I, and uncondensed vapor phase components are a mixture of the light components and ammonia and are sent to a tail gas treatment system;
mixed liquid of tert-butyl alcohol, water, ammonia and cyclohexanone oxime is obtained at the bottom of the rectifying tower I (2), one part of the mixed liquid enters the cold side of a reboiler (4) at the bottom of the rectifying tower I, the mixed liquid returns to the rectifying tower I (2) after heat exchange, and the other part of the mixed liquid is extracted and sent to a rectifying tower II (5);
b. the bottom discharge of the rectifying tower I (2) enters a rectifying tower II (5) for rectification treatment, mixed steam II containing tert-butyl alcohol, water and ammonia is obtained at the top of the rectifying tower II (5), enters the hot side of a rectifying tower II condenser (8), is condensed to obtain a recovered solvent II, one part of the recovered solvent II is returned to the rectifying tower II (5) from the top of the rectifying tower as reflux liquid, and the other part of the recovered solvent II is extracted and returned to the ammoximation process together with the recovered solvent I for recycling;
heat pump working medium liquid on the cold side of a condenser (8) of a rectifying tower II exchanges heat with mixed steam II to generate heat pump working medium steam, the heat pump working medium steam is pressurized by a compressor (6) to improve the energy grade and then enters the hot side of a reboiler (7) at the bottom of the rectifying tower II to provide a heat source for the reboiler (7) at the bottom of the rectifying tower II and simultaneously exchange heat and condense to obtain heat pump working medium liquid, and the heat pump working medium liquid returns to the cold side of the condenser (8) of the rectifying tower II to form heat pump circulation;
and (3) obtaining cyclohexanone oxime aqueous solution at the bottom of the rectifying tower II (5), allowing one part of the cyclohexanone oxime aqueous solution to enter the cold side of a reboiler (7) at the bottom of the rectifying tower II, returning the cyclohexanone oxime aqueous solution to the rectifying tower II (5) after heat exchange, and extracting the other part of the cyclohexanone oxime aqueous solution to be sent to a subsequent process.
9. The method according to claim 8, wherein the preheated ammoximation reaction product is preheated by taking any one or more of recovered solvent II, extracted cyclohexanone oxime aqueous solution, mixed steam I and steam condensate discharged after heat exchange of a hot side of a reboiler (4) at the bottom of the rectifying tower I as a heat source.
10. The method according to claim 9, characterized in that the rectifier I bottom reboiler (4) is heated with raw steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110534471.0A CN113121313A (en) | 2021-05-17 | 2021-05-17 | Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110534471.0A CN113121313A (en) | 2021-05-17 | 2021-05-17 | Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113121313A true CN113121313A (en) | 2021-07-16 |
Family
ID=76782003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110534471.0A Pending CN113121313A (en) | 2021-05-17 | 2021-05-17 | Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113121313A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126374A (en) * | 2015-06-29 | 2015-12-09 | 天津市天地创智科技发展有限公司 | tert-Butanol-water-cyclohexanone oxime differential-pressure rectification system |
| CN205549650U (en) * | 2016-03-14 | 2016-09-07 | 江苏乐科节能科技股份有限公司 | Heat pump rectification system |
| CN111138246A (en) * | 2019-12-30 | 2020-05-12 | 聊城鲁西聚酰胺新材料科技有限公司 | Energy-saving process for recycling tertiary butanol in ammoximation reaction |
| CN111302899A (en) * | 2020-04-14 | 2020-06-19 | 湖南百利工程科技股份有限公司 | Device and method for recovering ammonia and tert-butyl alcohol in cyclohexanone ammoximation production process |
-
2021
- 2021-05-17 CN CN202110534471.0A patent/CN113121313A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126374A (en) * | 2015-06-29 | 2015-12-09 | 天津市天地创智科技发展有限公司 | tert-Butanol-water-cyclohexanone oxime differential-pressure rectification system |
| CN205549650U (en) * | 2016-03-14 | 2016-09-07 | 江苏乐科节能科技股份有限公司 | Heat pump rectification system |
| CN111138246A (en) * | 2019-12-30 | 2020-05-12 | 聊城鲁西聚酰胺新材料科技有限公司 | Energy-saving process for recycling tertiary butanol in ammoximation reaction |
| CN111302899A (en) * | 2020-04-14 | 2020-06-19 | 湖南百利工程科技股份有限公司 | Device and method for recovering ammonia and tert-butyl alcohol in cyclohexanone ammoximation production process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107628930A (en) | A kind of heat pump separation of extractive distillation methanol, the energy saving technique of isopropyl alcohol and water | |
| CN109369444A (en) | Dimethylformamide is from backheat distillation system and recovery method | |
| CN110218147A (en) | Utilize the tert-butyl alcohol recovery method of cyclohexanone oxamidinating reaction heat | |
| CN111333484A (en) | Ultrahigh-purity methane chloride production system and process | |
| CN113121314B (en) | Device and method for recycling tertiary butanol by combining dividing wall rectifying tower with heat pump technology | |
| CN212102639U (en) | Device for refining cyclohexanone by cyclohexanol dehydrogenation | |
| CN215975597U (en) | Energy-saving recovery device for ammoximation reaction solvent tert-butyl alcohol by using open or closed heat pump | |
| CN212102640U (en) | System for preparing acetic anhydride by acetic acid cracking-ketene method | |
| CN108083984A (en) | For glyphosate solvent and the method for by-product recovery | |
| CN215712710U (en) | Device for recovering tert-butanol by using dividing wall rectifying tower combined with open or closed heat pump | |
| CN113121313A (en) | Energy-saving recovery device and method for tertiary butanol serving as ammoximation reaction solvent | |
| CN106699503B (en) | Energy-saving thermal chlorination process | |
| CN214781576U (en) | Caprolactam rearrangement heat energy cyclic utilization device | |
| CN210495282U (en) | Four-tower distillation and membrane separation integrated system | |
| CN212425916U (en) | Ultra-high-purity methane chloride production system | |
| CN215975598U (en) | Device for refining cyclohexanone by cyclohexanol dehydrogenation | |
| CN111848482A (en) | Separation method of cyclohexanone oxime gas phase reaction rearrangement product | |
| CN110711400A (en) | Energy-saving caprolactam production system and method by evaporating caprolactam water solution | |
| CN218834038U (en) | Novel acrylic acid reaction gas separation system | |
| CN220478784U (en) | Gas phase reaction system utilizing waste heat | |
| CN212119075U (en) | Acetyl n-propanol product purification device | |
| CN219518802U (en) | Foaming agent production tail gas draws urea reuse system | |
| CN221244008U (en) | Methanol rectification waste heat utilization system | |
| CN220478146U (en) | Device for producing caprolactam and co-producing 6-aminocapronitrile | |
| CN107434757A (en) | A kind of method and device of super low energy consumption recovery caprolactam organic extractant |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210716 |