CN113307721B - Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone - Google Patents
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone Download PDFInfo
- Publication number
- CN113307721B CN113307721B CN202110668903.7A CN202110668903A CN113307721B CN 113307721 B CN113307721 B CN 113307721B CN 202110668903 A CN202110668903 A CN 202110668903A CN 113307721 B CN113307721 B CN 113307721B
- Authority
- CN
- China
- Prior art keywords
- dichloroacetophenone
- dichlorobenzene
- pressure
- product
- organic phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Abstract
The invention discloses a method for recycling 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone, which comprises the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, adding sodium hydroxide and deionized water, and performing high-pressure decomposition and layering to obtain a crude product of m-dichlorobenzene; washing the m-dichlorobenzene crude product to obtain an m-dichlorobenzene product; the m-dichlorobenzene product is recycled and reused. The recycling process is simple, the equipment investment is low, the operation is convenient, the content of the recycled product is high, the resource waste is avoided, and the production cost is greatly saved.
Description
Technical Field
The invention relates to the field of organic synthetic chemistry, in particular to recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone.
Background
2, 4-dichloro acetophenone is an important fine chemical intermediate, is a raw material for preparing omega-bromo-2, 4-dichloro acetophenone or omega-2, 4-trichloroacetophenone, is mainly used for synthesizing fungicides such as imazalil, propiconazole and etaconazole, insecticides such as chlorfenvinphos and herbicides such as difenzoquat, and has wide application in the fields of medicines, pesticides and the like.
At present, m-dichlorobenzene is used as a raw material for synthesizing 2, 4-dichloroacetophenone, acetyl chloride is used as an acylating agent in a cyclohexane solution, aluminum trichloride is used as a catalyst, Fridel-Crafts acylation is carried out to obtain a crude product of the 2, 4-dichloroacetophenone, hydrolysis and layering are carried out after the reaction is finished, a water layer is removed, an organic phase is collected, cyclohexane of the organic phase is removed, rectification is carried out on the organic phase, and the top fraction is 2, 4-dichloroacetophenone.
The chemical synthesis reaction of 2, 4-dichloro acetophenone is as follows:
the process of producing 2, 4-dichloroacetophenone by using m-dichlorobenzene as a raw material and acetic anhydride as an acylating agent has side reaction to produce the isomer 2, 6-dichloroacetophenone with the proportion of 5%.
The side reaction in the chemical synthesis of 2, 4-dichloroacetophenone is as follows:
in the traditional recovery treatment method, the by-products are not recovered, but the tower bottom materials after rectification are directly treated as three wastes, so that the consumption of the produced raw materials is high, and the waste of the raw materials is serious.
Disclosure of Invention
In view of the above, the invention provides recycling of 2, 4-dichloroacetophenone isomer, 2, 6-dichloroacetophenone, so as to solve the problems of no effective treatment of byproducts and resource waste in the production process of 2, 4-dichloroacetophenone in the prior art, and the method provided by the invention can be used for reprocessing, recycling and reusing the 2, 4-dichloroacetophenone isomer, 2, 6-dichloroacetophenone, and converting the product, 2, 4-dichloroacetophenone, so that resource waste is avoided, and the production cost is greatly saved.
The invention provides the following technical scheme:
the recycling of 2, 6-dichloroacetophenone isomer comprises the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, adding sodium hydroxide and deionized water, and performing high-pressure decomposition and layering to obtain a crude product of m-dichlorobenzene; washing the m-dichlorobenzene crude product to obtain an m-dichlorobenzene product; the m-dichlorobenzene product is recycled and reused.
Preferably, the tower bottom residue containing the 2, 6-dichloroacetophenone is a kettle bottom residue obtained after the rectification of the crude product of the 2, 4-dichloroacetophenone by removing the organic solvent; the 2, 4-dichloroacetophenone crude product is synthesized by taking m-dichlorobenzene and acetyl chloride as raw materials and aluminum trichloride as a catalyst through reaction.
Preferably, the bottoms comprise 2, 4-dichloroacetophenone, 2, 6-dichloroacetophenone, and other impurities.
Preferably, the high-pressure decomposition specifically comprises the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, and adding sodium hydroxide and deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.2-1.6 MPa, and then heating to 200-280 ℃; when the pressure of the system naturally rises to 3.5-5.5 MPa, the temperature and the pressure are kept for 2-5 hours, then the temperature is reduced to 30-50 ℃, when the pressure of the system is reduced to 1.2-1.6 MPa, an emptying valve is opened, and the stirring is stopped.
Preferably, the washing of the crude m-dichlorobenzene product specifically comprises the following steps: standing the material subjected to high-pressure decomposition for half an hour, and separating a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using a hydrochloric acid solution, and then layering to obtain an organic phase; washing the organic phase once with deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
More preferably, the concentration of the hydrochloric acid solution is 3%.
Preferably, the recycling of the 2, 4-dichloroacetophenone isomer, 2, 6-dichloroacetophenone, comprises the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, and adding sodium hydroxide and deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.5MPa, then heating to 250 ℃, naturally increasing the system pressure to 4.5MPa, preserving the heat at the temperature and the pressure for 3 hours, then cooling to 40 ℃, opening an emptying valve when the system pressure is reduced to 1.5MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using a hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; washing the organic phase once with deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
Preferably, the content of the m-dichlorobenzene product is 97.9-98.7%.
According to the technical scheme, the invention has the beneficial effects that:
(1) the method uses m-dichlorobenzene and acetyl chloride as raw materials to recycle the 2, 4-dichloroacetophenone isomer, namely the 2, 6-dichloroacetophenone, which is a main byproduct generated in the production of the 2, 4-dichloroacetophenone, and has the advantages of simple process, less equipment investment, convenient operation and high content of recycled products.
(2) The recycling of the 2, 4-dichloroacetophenone isomer, namely the 2, 6-dichloroacetophenone, solves the problem that the 2, 6-dichloroacetophenone is directly treated as hazardous waste in the traditional production process, realizes the comprehensive utilization of solid waste resources, avoids environmental pollution and obviously reduces the original unit consumption of the 2, 4-dichloroacetophenone production.
(3) The product recovered by the method is an m-dichlorobenzene product, can be used as a raw material for producing 2, 4-dichloroacetophenone again, is recovered and reused, saves the production cost, and improves the effective utilization rate of the raw material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a process flow diagram for the recovery and utilization of 2, 4-dichloroacetophenone isomer, 2, 6-dichloroacetophenone, in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments and accompanying drawings. The exemplary embodiments and descriptions of the present invention are provided to explain the present invention, but not to limit the present invention.
Example 1
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone
500g of tower kettle residue containing 2, 6-dichloroacetophenone is distilled and pumped into an autoclave, the tower kettle residue comprises 5.3g of 2, 4-dichloroacetophenone and 472g of 2, 6-dichloroacetophenone, and the rest is other impurities; then adding 14g of sodium hydroxide and 28g of deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.2MPa, then heating to 200 ℃, naturally increasing the system pressure to 3.5MPa, preserving the heat at the temperature and the pressure for 3 hours, then cooling to 30 ℃, opening an emptying valve when the system pressure is reduced to 1.2MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using 200g of hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; and washing the organic phase once with 200g of deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
In this example, the mass of the m-dichlorobenzene product is 359 g; the content of m-dichlorobenzene product is 97.9%.
Example 2
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone
Distilling 500g of tower kettle residue containing 2, 6-dichloroacetophenone, pumping into an autoclave, wherein the tower kettle residue comprises 7.6g of 2, 4-dichloroacetophenone, 472.6g of 2, 6-dichloroacetophenone and the balance of other impurities; then adding 15g of sodium hydroxide and 30g of deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.3MPa, then heating to 220 ℃, naturally increasing the system pressure to 4MPa, preserving the heat at the temperature and the pressure for 3 hours, then cooling to 35 ℃, opening an emptying valve when the system pressure is reduced to 1.3MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using 200g of hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; and washing the organic phase once with 200g of deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
In this embodiment, the mass of the m-dichlorobenzene product is 364 g; the content of m-dichlorobenzene product is 98.2%.
Example 3
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone
500g of tower kettle residue containing 2, 6-dichloroacetophenone is distilled and pumped into an autoclave, wherein the tower kettle residue comprises 2.8g of 2, 4-dichloroacetophenone and 478g of 2, 6-dichloroacetophenone, and the rest is other impurities; then adding 16g of sodium hydroxide and 28g of deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.5MPa, then heating to 250 ℃, naturally increasing the system pressure to 4.5MPa, preserving the heat at the temperature and the pressure for 3 hours, then cooling to 40 ℃, opening an emptying valve when the system pressure is reduced to 1.5MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using 200g of hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; and washing the organic phase once with 200g of deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
In this example, the mass of the m-dichlorobenzene product is 367 g; the content of m-dichlorobenzene product is 98.5%.
Example 4
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone
500g of tower bottom residue containing 2, 6-dichloroacetophenone is distilled and pumped into an autoclave, the tower bottom residue comprises 6.9g of 2, 4-dichloroacetophenone and 473g of 2, 6-dichloroacetophenone, and the rest is other impurities; then adding 15g of sodium hydroxide and 25g of deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.4MPa, then heating to 260 ℃, naturally increasing the system pressure to 5MPa, preserving the heat at the temperature and the pressure for 4 hours, then cooling to 45 ℃, opening an emptying valve when the system pressure is reduced to 1.4MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using 200g of hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; and washing the organic phase once with 200g of deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
In this embodiment, the mass of the m-dichlorobenzene product is 364 g; the content of m-dichlorobenzene product is 98.3%.
Example 5
Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone
500g of tower kettle residue containing 2, 6-dichloroacetophenone is distilled and pumped into an autoclave, wherein the tower kettle residue comprises 3.5g of 2, 4-dichloroacetophenone and 481g of 2, 6-dichloroacetophenone, and the rest is other impurities; then adding 18g of sodium hydroxide and 32g of deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.6MPa, then heating to 280 ℃, naturally increasing the system pressure to 5.5MPa, preserving the heat at the temperature and the pressure for 5 hours, then cooling to 50 ℃, opening an emptying valve when the system pressure is reduced to 1.6MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using 200g of hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; and washing the organic phase once with 200g of deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
In this example, the mass of m-dichlorobenzene product is 371 g; the content of m-dichlorobenzene product is 98.7%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made to the embodiment of the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
- The recycling method of the 2, 6-dichloroacetophenone isomer is characterized by comprising the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, adding sodium hydroxide and deionized water, and performing high-pressure decomposition and layering to obtain a crude product of m-dichlorobenzene; washing the m-dichlorobenzene crude product to obtain an m-dichlorobenzene product; recycling the m-dichlorobenzene product; the high-pressure decomposition specifically comprises the following steps: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, and adding sodium hydroxide and deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.2-1.6 MPa, and then heating to 200-280 ℃; when the pressure of the system naturally rises to 3.5-5.5 MPa, the temperature and the pressure are kept for 2-5 hours, then the temperature is reduced to 30-50 ℃, when the pressure of the system is reduced to 1.2-1.6 MPa, an emptying valve is opened, and the stirring is stopped.
- 2. The recycling of 2, 4-dichloroacetophenone isomer, 2, 6-dichloroacetophenone, as claimed in claim 1, characterized in that the residue of the 2, 6-dichloroacetophenone-containing column is the residue of the bottom obtained by rectifying the crude 2, 4-dichloroacetophenone without organic solvent; the 2, 4-dichloroacetophenone crude product is synthesized by taking m-dichlorobenzene and acetyl chloride as raw materials and aluminum trichloride as a catalyst through reaction.
- 3. The recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone according to claim 1 wherein the column bottoms comprise 2, 4-dichloroacetophenone, 2, 6-dichloroacetophenone, and other impurities.
- 4. The recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone according to claim 1, characterized in that the washing of the crude m-dichlorobenzene product specifically comprises the following steps: standing the material subjected to high-pressure decomposition for half an hour, and separating a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using a hydrochloric acid solution, and then layering to obtain an organic phase; washing the organic phase once with deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
- 5. The recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone according to claim 4, characterized in that the concentration of the hydrochloric acid solution is 3%.
- 6. The recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone according to claim 1 comprising the steps of: distilling the residue in the tower kettle containing 2, 6-dichloroacetophenone, pumping into an autoclave, and adding sodium hydroxide and deionized water; closing the autoclave, starting stirring, pumping high-pressure air, keeping the pressure at 1.5MPa, then heating to 250 ℃, naturally increasing the system pressure to 4.5MPa, preserving the heat at the temperature and the pressure for 3 hours, then cooling to 40 ℃, opening an emptying valve when the system pressure is reduced to 1.5MPa, and stopping stirring; standing the reaction system for half an hour, and separating out a lower organic phase to obtain a crude m-dichlorobenzene product; washing the m-dichlorobenzene crude product once by using a hydrochloric acid solution with the concentration of 3%, and standing for layering to obtain an organic phase; washing the organic phase once with deionized water, standing for layering, and collecting the lower organic phase to obtain the m-dichlorobenzene product.
- 7. The recycling of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone of claim 1, characterized in that the content of the m-dichlorobenzene product is 97.9% -98.7%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110668903.7A CN113307721B (en) | 2021-06-16 | 2021-06-16 | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110668903.7A CN113307721B (en) | 2021-06-16 | 2021-06-16 | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113307721A CN113307721A (en) | 2021-08-27 |
CN113307721B true CN113307721B (en) | 2022-04-26 |
Family
ID=77378947
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110668903.7A Active CN113307721B (en) | 2021-06-16 | 2021-06-16 | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113307721B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113956136B (en) * | 2021-10-15 | 2023-07-04 | 浙江禾本科技股份有限公司 | Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA868400A (en) * | 1971-04-13 | Medema Dirk | Process for the preparation of 2,4-disubstituted phenyl ketones | |
DE1247289B (en) * | 1966-04-05 | 1967-08-17 | Shell Int Research | Process for the preparation of 2, 4- and 2, 5-dichloroacetophenone and trichloroacetophenones |
DE10249748A1 (en) * | 2002-10-25 | 2004-05-06 | Clariant Gmbh | Process for the preparation of 1,3-dihalogen-substituted benzene derivatives |
CN101898947A (en) * | 2010-08-19 | 2010-12-01 | 江苏隆昌化工有限公司 | Method for producing 2,4-dichloroacetophenone by using solid waste chlorobenzene tar as raw material |
-
2021
- 2021-06-16 CN CN202110668903.7A patent/CN113307721B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN113307721A (en) | 2021-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102898405B (en) | Process for preparing epoxypropane by directly using epoxidation propylene through hydrogen peroxide | |
CN108840310B (en) | Device and process for producing hydrogen chloride by deep analysis from dilute hydrochloric acid | |
CN101717335B (en) | Method for recovering DEIP in TDI residues | |
CN108911960A (en) | A kind of preparation method of photoinitiator 1- hydroxycyclohexyl phenyl ketone | |
CN109456204B (en) | Preparation method of gamma-methoxypropylamine | |
CN113307721B (en) | Recovery and utilization of 2, 4-dichloroacetophenone isomer 2, 6-dichloroacetophenone | |
CN105130778A (en) | Production process of methyl isobutyl ketone | |
CN214399818U (en) | Device for purifying hydrogen chloride by calcium chloride method containing impurity dilute hydrochloric acid | |
CN102659590A (en) | Alcoholysis recovery method of waster polylactic acid in ionic liquid environment | |
CN101045682A (en) | Method for retrieving organic acid, ester from cyclic ethane oxidation liquid | |
CN103183618A (en) | Method for recovering dimethylamine from dimethylamine hydrochloride | |
CN109134198A (en) | A kind of method of separation of extractive distillation tetrafluoropropanol and water azeotropic mixture | |
CN102161008B (en) | Method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene | |
CN104276937A (en) | Method for preparing adipic acid and C4-6-dibasic acid from cyclohexane oxidation reaction byproduct | |
CN108383082B (en) | Device and method for separating by-products generated in preparation of hydroxylamine hydrochloride by hydrolysis of nitromethane | |
CN114835569B (en) | Method for producing photoinitiator UV-184 by condensation method | |
CN111362778B (en) | Gas-phase desorption separation process of glycerol distillate | |
CN113735717A (en) | Treatment method of 37% nitric acid in pendimethalin process | |
CN106631651A (en) | Preparation method of benzyl methylbenzene | |
CN113956136B (en) | Recycling method of 2-chloro-4- (4-chlorophenoxy) acetophenone residues | |
CN104098438A (en) | Method for separating and recovering n-amyl alcohol from cyclohexanone by-product light oil | |
CN108059585B (en) | Preparation method of 2-methyl-1-ethynyl-2-penten-1-ol | |
CN219185851U (en) | Recovery system of waste material in continuous production N, N-diethyl formamide industrialization device | |
CN115466164B (en) | Process for producing o-phenylphenol | |
CN113666800B (en) | Synthesis method of 4-pentyne-1-alcohol |
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 |