CN113121311A - Comprehensive recovery treatment process of aniline tar - Google Patents
Comprehensive recovery treatment process of aniline tar Download PDFInfo
- Publication number
- CN113121311A CN113121311A CN201911415275.0A CN201911415275A CN113121311A CN 113121311 A CN113121311 A CN 113121311A CN 201911415275 A CN201911415275 A CN 201911415275A CN 113121311 A CN113121311 A CN 113121311A
- Authority
- CN
- China
- Prior art keywords
- tower
- tar
- rectifying tower
- aniline
- catalyst
- 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.)
- Granted
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/0035—Periodical feeding or evacuation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/20—Refining by chemical means inorganic or organic compounds
- C10C1/205—Refining by chemical means inorganic or organic compounds refining in the presence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of comprehensive recycling of chemical waste materials, and particularly relates to a comprehensive recycling treatment process of aniline tar in aniline production. The comprehensive recovery processing technology of aniline tar provided by the invention comprises the steps of mixing aniline tar and an organic solvent at least containing organic acid, introducing the mixture into a rectifying tower for hydrogenation processing, wherein the tar can generate cracking reaction to generate corresponding small molecular components such as ketoamine and the like under the action of a catalyst and the organic solvent at the upper section of the rectifying tower, the hydrogenation of a tar cracking product is realized at the lower section of the rectifying tower, and the generated components such as alcohol amine and the like and the catalyst are discharged from the bottom of the rectifying tower together. According to the process, tar is changed into components with small molecular weight through hydrocracking, so that high-economic-value products such as alcohol amine and the like are obtained, the toxic effect of the tar on the activity of the catalyst is solved, the activity of the separated noble metal catalyst can be effectively recovered and can be returned to the device, the catalyst can be recycled, and the comprehensive utilization benefit of the device is improved.
Description
Technical Field
The invention belongs to the technical field of comprehensive recycling of chemical waste materials, and particularly relates to a comprehensive recycling treatment process of aniline tar in aniline production, in particular to a treatment process of aniline tar and a recycling process of a catalyst.
Background
The aniline compound is an important chemical raw material and is widely applied to the fields of production of dye intermediates, medicines, pesticides, rubber auxiliaries, antioxidants, fine chemical intermediates and the like. At present, industrialized aniline compounds are mainly prepared by reducing nitro compounds, and the main synthesis methods comprise a metal reduction method, an alkali sulfide reduction method, an electrochemical reduction method, a catalyst hydrogenation method and the like, wherein the catalyst hydrogenation method has the advantages of better industrialized optimization, simple reaction process, high selectivity, high product purity and the like. Currently, the industrialized aniline production is mainly generated by reacting nitrobenzene and hydrogen under the catalytic action of a noble metal catalyst. The reaction form of the process mainly comprises a slurry bed, a reaction kettle and the like, and the subsequent separation of reaction products and the catalyst usually adopts a thickener, a candle filter and other devices.
Like many chemical reaction processes, byproducts such as cyclohexanone and tar are inevitably generated in the aniline production process, and part of the noble metal catalyst is also inevitably separated and flows out of the distillation tower along with heavy components (aniline tar) in the product separation process, so that the loss of the catalyst is caused. In order to reduce the influence of the by-products such as cyclohexanone on the product quality, cyclohexanone and the like are generally converted into heavy components such as Schiff base in the subsequent process, so as to reduce the influence on the product quality. But instead. The existence of the heavy component can cause the blockage of the catalyst pore channels, and the activity of the catalyst is greatly reduced. For the loss of the catalyst, most of the current reaction processes and reaction devices have no effective recovery process for the lost catalyst, and the lost catalyst is mainly directly incinerated in an incinerator along with the discharge of tar, so that the waste of the noble metal catalyst is caused on one hand, and the environmental pollution is caused on the other hand.
At present, the regeneration treatment of the noble metal catalyst is generally adopted in the reported treatment mode, namely, the noble metal in the catalyst is recovered and then is processed into a new catalyst to realize recycling. For example, the regeneration method of the Pt/C catalyst disclosed in Chinese patent CN103657683A is to treat the deactivated catalyst with hydrogen peroxide solution, then to obtain the regenerated Pt/C catalyst for reuse through impregnation and precipitation, and metal supplement. For another example, chinese patent CN102766767A discloses a method for recovering precious metals in a catalyst by dissolving aqua regia, adsorbing platinum by ion resin exchange, and desorbing platinum by concentrated sulfuric acid. For another example, chinese patent CN101074458 discloses a method of dissolving a catalyst with hydrochloric acid or sulfuric acid for a long time, replacing with aluminum, then oxidizing and dissolving with hypochlorous acid and concentrated sulfuric acid, and finally separating and purifying. However, the above method generally employs strong acid and other substances, which are not only expensive and polluting the environment, but also dangerous and unfavorable for operation.
The aniline tar is a waste material in aniline production, and is a black viscous liquid with pungent smell at normal temperature, in the aniline tar, the light component is mainly aniline, and a small amount of cyclohexanone, methylaniline, phenol, diphenylamine and the like are also contained, and the heavy component is a long-chain oligomer of aniline. At present, aniline tar is mostly treated by incineration, but a large amount of nitrogen oxides are generated, so that certain atmospheric and environmental pollution is caused, and valuable components such as noble metal catalysts and the like are not recycled, so that great economic loss is caused.
Therefore, how to reasonably utilize the aniline tar as a resource can solve the problem of catalyst blockage, reduce environmental pollution, realize the recycling of the noble metal catalyst, change waste into valuable and have important environmental protection significance and economic value.
Disclosure of Invention
The invention aims to provide a comprehensive recovery treatment process of aniline tar, which can convert the aniline tar into useful components and realize the recovery and reutilization of a noble metal catalyst.
In order to solve the technical problems, the comprehensive recovery treatment process of aniline tar comprises the following steps:
(1) the aniline tar obtained by the reaction is concentrated, added with an organic solvent at least containing organic acid, mixed and then introduced into a rectifying tower, and hydrogen is introduced for hydrogenation reaction; the upper section of the rectifying tower realizes hydrocracking of heavy components such as tar and the like, and organic solvent-containing materials are obtained at the tower top of the rectifying tower; the lower section of the rectifying tower realizes the hydrogenation of the tar cracking product, and the catalyst and the cracking hydrogenation product are discharged from the tower bottom of the rectifying tower;
(2) collecting a tower bottom product of the rectifying tower, carrying out solid-liquid separation on the tower bottom product, conveying the obtained liquid phase product to a recovery tower for treatment, and directly returning the solid phase catalyst product to an aniline production device for recycling;
(3) in the recovery tower, light component products are obtained through the separation of the top of the tower, and heavy component products are obtained at the bottom of the tower.
Specifically, in the step (1), the organic solvent further includes a second solvent, and the mass ratio of the second solvent to the organic acid is controlled to be 100: 1-1000: 1, and preferably the mass ratio of the second solvent to the organic acid is 300: 1-800: 1.
specifically, in the comprehensive recovery treatment process of aniline tar:
the second solvent comprises at least one of isobutanol, n-butanol, toluene, benzene, nitroethane, cyclohexane, octane, ethyl acetate and dichloroethane;
the organic acid comprises at least one of C1-C4 organic acids.
Specifically, in the step (1):
the mass ratio of the organic solvent to the aniline tar is 5: 1-200: 1, and preferably the mass ratio of the organic solvent to the aniline tar is 20: 1-80: 1;
the feeding mass ratio of the hydrogen to the aniline tar is 1: 1-1: 50, and preferably 1: 5-1: 10.
specifically, in the step (1), the number of the plates of the rectifying tower is 30-85; the operation pressure at the top of the tower is controlled to be 0.1-1.5MPaA, the temperature at the bottom of the tower is 140-.
Preferably, the number of the plates of the rectifying tower is 45-75, the operation pressure at the top of the tower is 0.2-0.7MPaA, the temperature of the bottom of the tower is 180-320 ℃, and the reflux ratio at the top of the tower is 1-4.
Specifically, in the step (1), the feeding position of the organic solvent is positioned at the upper part of the rectifying tower, and preferably the feeding position is at 5-10 trays; the feeding position of the hydrogen is positioned at the lower part of the rectifying tower, and the feeding position is preferably positioned below the bottommost tower plate of the rectifying tower and above the outlet of the reboiler.
Specifically, the step (1) further comprises a step of introducing water into the middle part of the rectifying tower, wherein the distance between the feeding position of the water and the feeding position of the aniline tar is 25-35 trays;
controlling the feeding mass ratio of the water to the aniline tar to be 5: 1-1: 20, and preferably 1: 1-1: 5.
specifically, the step (1) further comprises the steps of performing two-phase separation on the light component material obtained at the top of the rectifying tower, and returning the separated water phase to the rectifying tower to be used as water supplement.
Specifically, in the step (2), the number of the tower plates of the recovery tower is 20-60, the operation pressure at the top of the tower is controlled to be 5-50KPaA, the temperature at the bottom of the tower is 100-.
Preferably, the tower plate number of the recovery tower is 30-50, and the operation pressure at the top of the tower is 10-30 KPaA; the temperature of the tower bottom is preferably 130 ℃ and 190 ℃, and the reflux ratio is 2-4.
Specifically, the step (2) further comprises a step of separating the catalyst, and specifically, at least one of filtration, centrifugation and decantation may be used.
Specifically, the step (3) further comprises a step of conveying the heavy component product obtained from the tower bottom to an incinerator for incineration treatment.
The comprehensive recovery processing technology of aniline tar comprises the steps of mixing concentrated aniline tar with an organic solvent at least containing organic acid, introducing the mixture into a rectifying tower for hydrogenation processing, wherein the tar is subjected to cracking reaction to generate corresponding small molecular components such as ketoamine and the like under the action of a catalyst and the organic solvent at the upper section of the rectifying tower, and in view of the boiling point difference of different solvents, light components contained in the organic solvent are discharged from the top of the rectifying tower, and after water is skimmed, part of oil phase is subjected to incineration processing, and part of oil phase is used as a raw material to be mixed with the tar; the lower section of the rectifying tower realizes the hydrogenation of tar cracking products, the components such as ketoamine and the like are subjected to hydrogenation reaction under the action of the catalyst, the generated components such as alcohol amine and the like and the catalyst are discharged from the bottom of the rectifying tower together, the separated catalyst can be directly returned to an aniline production device for recycling, the liquid-phase components enter a recovery tower to be refined to obtain high-purity alcohol amine materials, and the heavy-component products can be conveyed to an incinerator for incineration treatment.
According to the comprehensive recovery treatment process of aniline tar, tar is changed into components with small molecular weight through hydrocracking, so that high-economic-value products such as alcohol amine and the like are obtained, the viscosity of a system is effectively reduced, the toxic effect of tar on the activity of a catalyst is solved, the activity of the separated noble metal catalyst can be effectively recovered and can be returned to a device, the recovery rate of the catalyst in the whole process is more than 85%, the catalyst is really recycled, the consumption of the catalyst is greatly reduced, and the comprehensive utilization benefit of the device is improved. The process has the characteristics of short flow, less equipment, low energy consumption and less three wastes, is simple in industrial amplification, and has the advantages of environmental friendliness and high economic benefit.
According to the comprehensive recovery treatment process of aniline tar, the mixture of tar and an organic solvent is preferably introduced from the upper part of the rectifying tower, more preferably the feeding position is 5-10 tower plates, and hydrogen is preferably introduced from the bottom of the rectifying tower, so that the contact efficiency of reactants can be effectively improved, and the reaction efficiency is improved.
According to the comprehensive recovery treatment process of aniline tar, a stream of trace water is preferably introduced into the middle of the rectifying tower, so that the cracking speed of certain components in the tar can be effectively accelerated, and the cracking efficiency is further improved.
Drawings
FIG. 1 is a flow diagram of a recovery process according to the present invention.
Detailed Description
The following examples are provided to illustrate the embodiments of the present invention in further detail, and all examples are operated under the operating conditions of the above technical solutions, so as to better understand the contents of the present invention. The examples given therefore do not limit the scope of the invention.
Example 1
According to the process flow chart shown in figure 1, acetic acid and toluene are taken according to the mass ratio of 1: 500, preparing the organic solvent, and adopting a rectifying tower with 62 theoretical plates to mix the organic solvent and aniline tar according to a mass ratio of 50: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 10 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 2; the pressure of the top of the rectifying tower is 0.4MpaA, the temperature of the tower kettle is maintained at 257 ℃, and the reflux ratio is 2. Hydrocracking heavy components such as tar and the like at the upper section of the rectifying tower to obtain an organic solvent-containing material at the tower top of the rectifying tower; the lower section of the rectifying tower realizes the hydrogenation of the tar cracking products, and the catalyst and the cracking hydrogenation products are discharged from the tower bottom of the rectifying tower.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent and discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the rectifying tower runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst is greater than 85%, the recovered noble metal catalyst is directly used for nitrobenzene hydrogenation evaluation, the activity of the regenerated noble metal catalyst is analyzed to be 82% (based on the activity of the fresh catalyst being 100%), and the alcohol amine content in the liquid material filtered out from the column bottom is analyzed to be about 42%.
Taking the collected filtrate in the tower bottom of the rectifying tower as a raw material, carrying out a component recovery experiment, wherein the number of tower plates of the recovery tower is 47, and the raw material enters the recovery tower from the 28 th tower plate; the top pressure of the rectifying tower is controlled to be 15kpa, the temperature of the tower kettle is maintained to be 164 ℃, and the reflux ratio is 4. After the recovery tower runs stably, the alcohol amine content in the tower top sample is analyzed to be about 92%, and the calculated alcohol amine recovery rate is about 40%. And (4) conveying the heavy component product obtained from the tower kettle to an incinerator for incineration treatment.
Example 2
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different from that in embodiment 1 only in that the mass ratio of the organic solvent to the tar is controlled to be 70: 1, wherein the organic solvent is formic acid and toluene according to a mass ratio of 1: 700, controlling the temperature of the bottom of the distillation tower to be 242 ℃, the reflux ratio to be 2.5, and keeping the rest parameters and the rectification parameters unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the distillation tower device operates stably, collecting discharged components in the tower kettle, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 88% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 54 percent.
Component recovery was performed according to the same parameters as in example 1, analyzing the alcohol amine content in the overhead sample of the recovery column to be about 95%, and calculating the alcohol amine recovery to be about 53%.
Example 3
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different in that a rectifying tower with theoretical plate number of 75 is adopted, the mixture of the organic solvent and tar is controlled to enter the rectifying tower from a 7 th tower plate, hydrogen is introduced below the 75 th tower plate of the rectifying tower, a strand of water is introduced at a 42 th tower plate of the rectifying tower, the temperature of a tower kettle is controlled to be 240 ℃, the reflux ratio is 2, and other parameters and rectifying parameters are unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the device runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. The recovered noble metal catalyst is directly utilized to carry out nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst is analyzed to be 92 percent (by taking the activity of the fresh catalyst as 100 percent). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 63 percent.
Component recovery was performed according to the same parameters as in example 1, analyzing the alcohol amine content in the overhead sample of the recovery column to be about 97%, and calculating the alcohol amine recovery to be about 62%.
Example 4
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different in that a rectifying tower with 62 theoretical plates is adopted, hydrogen is introduced below 62 plates of the rectifying tower, the feeding amount of the hydrogen is controlled to be 14% of that of the tar, the temperature of a tower kettle is controlled to be 242 ℃, and other parameters and rectifying parameters are unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the device runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 89% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 58 percent.
The recovery of the components was carried out according to the same parameters as in example 1, and the alcohol amine content in the overhead sample of the analytical recovery column was about 95%, and the alcohol amine recovery rate was calculated to be about 56%.
Example 5
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different in that a rectifying tower with 62 theoretical plates is adopted, water is not supplemented in the rectifying tower, the temperature of a tower kettle is controlled to be 266 ℃, and other parameters and rectifying parameters are unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the device runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 70% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 25 percent.
Component recovery was performed according to the same parameters as in example 1, analyzing the alcohol amine content in the overhead sample of the recovery column to be about 93%, and calculating the alcohol amine recovery to be about 24%.
Example 6
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different in that a rectifying tower with 62 theoretical plates is adopted, and enters the rectifying tower from a 7 th tower plate, wherein the organic solvent is a toluene solution, the temperature of a tower kettle is controlled to be 261 ℃, and other parameters and rectifying parameters are unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the device runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 73% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 29 percent.
The recovery of the components was carried out according to the same parameters as in example 1, and the alcohol amine content in the overhead sample of the analytical recovery column was about 93%, and the alcohol amine recovery rate was calculated to be about 27%.
Example 7
The process for recovering and treating aniline tar in the embodiment is the same as that in embodiment 1, and is different in that the operating pressure of the rectifying tower is controlled to be 0.7MpaA, the temperature of the tower kettle is controlled to be 284 ℃, and other parameters and rectifying parameters are unchanged.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement.
And after the device runs stably, collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material. In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 84% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 46 percent.
Component recovery was performed according to the same parameters as in example 1, analyzing the alcohol amine content in the overhead sample of the recovery column to be about 95%, and calculating the alcohol amine recovery to be about 45%.
Example 8
Taking propionic acid and ethyl acetate according to a mass ratio of 1: 100, preparing the organic solvent, and adopting a rectifying tower with 62 theoretical plates to mix the organic solvent and aniline tar according to a mass ratio of 20: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 20 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 1; the pressure of the top of the rectifying tower is 0.2MpaA, the temperature of the bottom of the rectifying tower is kept at 210 ℃, and the reflux ratio is 1.5.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 94% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 66%.
The collected filtrate in the tower bottom of the rectifying tower is used as a raw material to carry out a component recovery experiment, the number of tower plates of the recovery tower is 30, the tower top pressure of the rectifying tower is controlled to be 20kpa, the temperature of the tower bottom is maintained to be 180 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the alcohol amine content in the top sample of the analytical recovery tower was about 96%, and the calculated alcohol amine recovery rate was about 64%.
Example 9
As shown in a process flow chart of fig. 1, butyric acid and benzene are taken according to a mass ratio of 1: 300, preparing the organic solvent, and mixing the organic solvent and aniline tar in a mass ratio of 80: 1, and enters a rectifying tower from the 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 2 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 1; the pressure of the top of the rectifying tower is 0.1MpaA, the temperature of the bottom of the rectifying tower is kept at 183 ℃, and the reflux ratio is 1.5.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 93% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 50 percent.
The collected filtrate in the tower bottom of the rectifying tower is used as a raw material to carry out a component recovery experiment, the number of tower plates of a recovery tower is 50, the tower top pressure of the rectifying tower is controlled to be 30kpa, the temperature of the tower bottom is maintained to be 186 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the content of the alcohol amine in the sample at the top of the analytical recovery tower was about 92%, and the calculated alcohol amine recovery rate was about 49%.
Example 10
As shown in a process flow chart of figure 1, taking acetic acid and n-butanol according to a mass ratio of 1: 800, preparing the organic solvent, and adopting a rectifying tower with 62 theoretical plates to mix the organic solvent with aniline tar according to a mass ratio of 5: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 50 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 5; the top pressure of the rectifying tower is 1.5MpaA, the temperature of the tower kettle is maintained at 334 ℃, and the reflux ratio is 4.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 80% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 39%.
The collected filtrate in the bottom of the rectifying tower is used as a raw material to carry out a component recovery experiment, the number of tower plates of a recovery tower is 50, the pressure of the top of the rectifying tower is controlled to be 30kpa, the temperature of the bottom of the rectifying tower is kept to be 197 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the alcohol amine content in the top sample of the analytical recovery tower was about 95%, and the calculated alcohol amine recovery rate was about 39%.
Example 11
As shown in a process flow chart of fig. 1, acetic acid and nitroethane are taken according to a mass ratio of 1: 1000, preparing the organic solvent, and mixing the organic solvent and aniline tar in a mass ratio of 200: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 25 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 20; the pressure of the top of the rectifying tower is 1.0MpaA, the temperature of the bottom of the rectifying tower is maintained to be 347 ℃, and the reflux ratio is 6.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 74% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 29 percent.
And (3) carrying out a component recovery experiment by taking the collected filtrate at the bottom of the rectifying tower as a raw material, wherein the number of tower plates of the recovery tower is 40, the tower top pressure of the rectifying tower is controlled to be 10kpa, the temperature of the bottom of the rectifying tower is maintained to be 159 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the content of the alcohol amine in the sample at the top of the analytical recovery tower is about 92%, and the calculated alcohol amine recovery rate is about 28%.
Example 12
As shown in a process flow chart of fig. 1, formic acid and dichloroethane are taken according to a mass ratio of 1: 500, preparing the organic solvent, and mixing the organic solvent and aniline tar in a mass ratio of 100: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 30 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 10; the pressure of the top of the rectifying tower is 1.2MpaA, the temperature of the bottom of the rectifying tower is kept at 318 ℃, and the reflux ratio is 3.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 77% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 33 percent.
The collected filtrate in the bottom of the rectifying tower is used as a raw material to carry out a component recovery experiment, the number of tower plates of the recovery tower is 30, the top pressure of the rectifying tower is controlled to be 50kpa, the temperature of the bottom of the rectifying tower is maintained to be 210 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the content of the alcohol amine in the sample at the top of the analytical recovery tower is about 90%, and the calculated alcohol amine recovery rate is about 31%.
Example 13
As shown in a process flow chart of fig. 1, formic acid and cyclohexane are taken according to a mass ratio of 1: 500, preparing the organic solvent, and mixing the organic solvent and aniline tar in a mass ratio of 500: 1, and enters a rectifying tower from a 7 th tower plate, and hydrogen is introduced below 62 tower plates of the rectifying tower, and the feeding amount of the hydrogen is controlled to be 15 wt% of that of the tar; introducing a strand of water at the 37 th tower plate of the rectifying tower, and controlling the feed mass ratio of the water to the tar to be 1: 15; the top pressure of the rectifying tower is 0.5MpaA, the temperature of the tower bottom is kept to be 247 ℃, and the reflux ratio is 2.
And after the rectifying tower runs stably, collecting a light component product containing the organic solvent discharged from the top of the tower, carrying out two-phase separation on the light component product, and returning the separated water phase to the rectifying tower for water supplement. And collecting discharged components at the bottom of the tower, and separating by adopting a suction filtration method to respectively obtain a solid precious metal catalyst sample and a liquid material.
In this example, the recovery rate of the catalyst was greater than 85%, and the recovered noble metal catalyst was directly used for nitrobenzene hydrogenation evaluation, and the activity of the regenerated noble metal catalyst was analyzed to be 78% (based on the activity of the fresh catalyst being 100%). The alcohol amine content in the liquid material filtered out from the bottom of the analysis tower is about 37 percent.
And (3) carrying out a component recovery experiment by taking the collected filtrate in the tower bottom of the rectifying tower as a raw material, wherein the number of tower plates of the recovery tower is 47, the tower top pressure of the rectifying tower is controlled to be 5kpa, the temperature of the tower bottom is maintained to be 153 ℃, and the reflux ratio is 4. And separating the tower top to obtain light component products such as cyclohexylamine, cyclohexanol and the like, and conveying the heavy component products obtained from the tower bottom to an incinerator for incineration treatment.
In this example, the alcohol amine content in the top sample of the analytical recovery tower was about 94%, and the calculated alcohol amine recovery rate was about 36%.
The above description is a preferred embodiment of the present invention, but the present invention is not limited to the disclosure of the embodiment. Any simple variation, modification or other equivalent substitution by a person skilled in the art without any inventive step falls within the scope of protection of the present invention, without leaving the core of the invention.
Claims (10)
1. The comprehensive recovery treatment process of aniline tar is characterized by comprising the following steps:
(1) the aniline tar obtained by the reaction is concentrated, added with an organic solvent at least containing organic acid, mixed and then introduced into a rectifying tower, and hydrogen is introduced for hydrogenation reaction; the upper section of the rectifying tower realizes hydrocracking of heavy components such as tar and the like, and organic solvent-containing materials are obtained at the tower top of the rectifying tower; the lower section of the rectifying tower realizes the hydrogenation of the tar cracking product, and the catalyst and the cracking hydrogenation product are discharged from the tower bottom of the rectifying tower;
(2) collecting a tower bottom product of the rectifying tower, carrying out solid-liquid separation on the tower bottom product, conveying the obtained liquid phase product to a recovery tower for treatment, and directly returning the solid phase catalyst product to an aniline production device for recycling;
(3) in the recovery tower, light component products are obtained through the separation of the top of the tower, and heavy component products are obtained at the bottom of the tower.
2. The process for comprehensively recovering and treating aniline tar according to claim 1, wherein in the step (1), the organic solvent further comprises a second solvent, and the mass ratio of the second solvent to the organic acid is controlled to be 100: 1-1000: 1.
3. the comprehensive recovery processing technology of aniline tar according to claim 2, characterized in that:
the second solvent comprises at least one of isobutanol, n-butanol, toluene, benzene, nitroethane, cyclohexane, octane, ethyl acetate and dichloroethane;
the organic acid comprises at least one of C1-C4 organic acids.
4. The process for the integrated recovery and treatment of aniline tar according to any one of claims 1 to 3, wherein in the step (1):
the mass ratio of the organic solvent to the aniline tar is 5: 1-200: 1;
the feeding mass ratio of the hydrogen to the aniline tar is 1: 1-1: 50.
5. the process for comprehensively recycling aniline tar according to any one of claims 1 to 4, characterized in that in the step (1), the number of the plates of the rectifying tower is 30 to 85; the operation pressure at the top of the tower is controlled to be 0.1-1.5MPaA, the temperature at the bottom of the tower is 140-.
6. The process for comprehensively recycling aniline tar according to any one of claims 1 to 5, characterized in that in step (1), the feeding position of the organic solvent is located at the upper part of the rectification column, and the feeding position of the hydrogen gas is located at the lower part of the rectification column.
7. The process for comprehensively recycling aniline tar according to any one of claims 1 to 6, characterized in that the step (1) further comprises a step of introducing water into the middle of the rectifying tower;
controlling the feeding mass ratio of the water to the aniline tar to be 5: 1-1: 20.
8. the process for comprehensively recycling aniline tar according to any one of claims 1 to 7, characterized in that the step (1) further comprises the steps of performing two-phase separation on the material obtained from the top of the rectification column and returning the separated water phase to the rectification column.
9. The process for comprehensively recovering and treating aniline tar according to any one of claims 1 to 8, wherein in the step (2), the number of the trays in the recovery tower is 20 to 60, the operation pressure at the top of the tower is 5 to 50KPaA, the temperature at the bottom of the tower is 100 ℃ and 250 ℃, and the reflux ratio is 1 to 7.
10. The process for comprehensively recovering and treating aniline tar according to any one of claims 1 to 9, wherein the step (3) further comprises the step of delivering the heavy component product obtained from the tower bottom to an incinerator for incineration treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911415275.0A CN113121311B (en) | 2019-12-31 | 2019-12-31 | Comprehensive recovery treatment process for aniline tar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911415275.0A CN113121311B (en) | 2019-12-31 | 2019-12-31 | Comprehensive recovery treatment process for aniline tar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113121311A true CN113121311A (en) | 2021-07-16 |
| CN113121311B CN113121311B (en) | 2022-09-20 |
Family
ID=76770487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911415275.0A Active CN113121311B (en) | 2019-12-31 | 2019-12-31 | Comprehensive recovery treatment process for aniline tar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113121311B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318280A (en) * | 2022-07-25 | 2022-11-11 | 万华化学（宁波）有限公司 | Method for regenerating and recycling catalyst and by-producing o-aminophenol from aniline tar |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3604705A1 (en) * | 1986-02-14 | 1987-08-27 | Bayer Antwerpen Nv | METHOD FOR THE TREATMENT OF 2-MERCAPTOBENZTHIAZOL CONTAINING TARS |
| CN101121633A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for reclaiming and purifying styrene |
| CN102701994A (en) * | 2012-06-01 | 2012-10-03 | 中国科学院研究生院 | Process method for separating and refining rough aniline |
| CN109550501A (en) * | 2018-11-08 | 2019-04-02 | 万华化学集团股份有限公司 | A kind of preparation method and applications of nitrobenzene liquid-phase hydrogenatin catalyst in aniline |
| CN109721469A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of cyclopentanone |
| CN110372509A (en) * | 2019-07-19 | 2019-10-25 | 江门谦信化工发展有限公司 | A kind of cracking recovery process of n-butyl acrylate heavy constituent |
-
2019
- 2019-12-31 CN CN201911415275.0A patent/CN113121311B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3604705A1 (en) * | 1986-02-14 | 1987-08-27 | Bayer Antwerpen Nv | METHOD FOR THE TREATMENT OF 2-MERCAPTOBENZTHIAZOL CONTAINING TARS |
| CN101121633A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for reclaiming and purifying styrene |
| CN102701994A (en) * | 2012-06-01 | 2012-10-03 | 中国科学院研究生院 | Process method for separating and refining rough aniline |
| CN109721469A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of cyclopentanone |
| CN109550501A (en) * | 2018-11-08 | 2019-04-02 | 万华化学集团股份有限公司 | A kind of preparation method and applications of nitrobenzene liquid-phase hydrogenatin catalyst in aniline |
| CN110372509A (en) * | 2019-07-19 | 2019-10-25 | 江门谦信化工发展有限公司 | A kind of cracking recovery process of n-butyl acrylate heavy constituent |
Non-Patent Citations (1)
| Title |
|---|
| 刘辉等: "CeO_2改性NiO/γ-Al_2O_3催化剂的苯胺焦油加氢轻质化", 《南京工业大学学报(自然科学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115318280A (en) * | 2022-07-25 | 2022-11-11 | 万华化学（宁波）有限公司 | Method for regenerating and recycling catalyst and by-producing o-aminophenol from aniline tar |
| CN115318280B (en) * | 2022-07-25 | 2023-05-30 | 万华化学（宁波）有限公司 | Method for regenerating and recovering catalyst and byproduct o-aminophenol from aniline tar |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113121311B (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100447118C (en) | Extraction and rectification separation method for normal hexane and methyl cyclopentane | |
| CN106977380B (en) | At low pressure CO2Method for preparing cyclohexanone by phenol hydrogenation in environment | |
| CN104909984B (en) | A kind of method reclaiming Hexalin from pimelinketone device waste liquid | |
| US7557252B2 (en) | Process for producing dihydroxybenzene and diisopropylbenzendicarbinol | |
| CN113121311B (en) | Comprehensive recovery treatment process for aniline tar | |
| CN111892477A (en) | Method for preparing aromatic hydrocarbon by hydrocracking aromatic ring-containing polymer | |
| CN106008186A (en) | Method for separating acetone, isopropanol and water mixed solution | |
| CN107324334B (en) | Method for producing phosgene from diphosgene or triphosgene | |
| CN102492845A (en) | Method for digesting spent rhodium catalyst in carbonyl group synthetic reaction | |
| CN113735688B (en) | Recycling method of waste liquid of butanol device | |
| CN109608418A (en) | A method of making hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane using tower reactor | |
| CN1048920C (en) | Catalyst regenerating method for synthesizing 1,4-butynediol from formaldehyde and acetylene by slurry-bed reaction | |
| US7122701B2 (en) | Process for preparing aromatic amines | |
| CN114345879A (en) | Chemical hazardous waste comprehensive utilization device and process | |
| CN113429258A (en) | Method for separating dichlorotoluene mixture | |
| CN106810433A (en) | A kind of method for producing cyclohexanone as raw material with coking benzene | |
| CN101817727A (en) | Treatment method of front cut fractions during production process of o-phenyl phenol | |
| JP2008169205A (en) | Production process and reactor for aromatic amine | |
| CN115318280B (en) | Method for regenerating and recovering catalyst and byproduct o-aminophenol from aniline tar | |
| CN106518810B (en) | Method for purifying propylene oxide | |
| CN112723992B (en) | Process for preparing high-purity decanediol by side-line vacuum rectification | |
| CN104084206A (en) | Aromatic amine hydrogenation catalyst recycling method | |
| JP2009007288A (en) | Cleaning method for solid matter and purification method for meta-cresol | |
| CN112876438B (en) | Separation and purification method of high-purity 3-acetamido-5-acetylfuran | |
| CN109456166B (en) | Method for preparing dibasic acid by using cyclohexane oxidation by-product X oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |