Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/08—Silica
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/652—Chromium, molybdenum or tungsten
  • B01J23/6527—Tungsten
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
  • C07C69/12—Acetic acid esters
  • C07C69/14—Acetic acid esters of monohydroxylic compounds
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/30—Tungsten
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/652—Chromium, molybdenum or tungsten

Definitions

• the present invention relates to a method for producing ethyl acetate using a catalyst in which a heteropolyacid or a salt thereof is supported on a carrier.
• Patent Documents 2 to 6 As one of the solutions for suppressing the deterioration of the catalyst in the synthesis reaction of esters using a supported heteropolyacid catalyst, acetylenes, halogens, aldehydes, basic nitrogen compounds, and metals or metal compounds contained in the feedstock are It is known to make it substantially free (Patent Documents 2 to 6).
• the reaction may proceed with low concentrations of precious metals on the order of ppm by mass or ppb by mass contained in raw materials, laboratory equipment, and industrial-scale manufacturing equipment.
• Non-Patent Document 1 reports that the Suzuki-Miyaura coupling reaction proceeds with the ppb-order mass of palladium contained in sodium carbonate.
• Non-Patent Document 2 reports that the Suzuki-Miyaura coupling reaction proceeds with a very small amount of metal contained in a used PTFE stirrer.
• JP-A-09-118647 Japanese Patent Application Laid-Open No. 2004-18404 JP-A-2004-83473 JP-A-11-269126 Japanese Patent Publication No. 2002-520380 Japanese Patent Publication No. 2002-520381
• the present invention provides a method for producing ethyl acetate in which ethylene and acetic acid are reacted, and which suppresses the progress of side reactions and enables continuous and stable operation for a long period of time. .
• the present inventors have found that in a method for producing ethyl acetate in which ethylene and acetic acid are reacted in the presence of a catalyst in which a heteropolyacid or a salt thereof is supported on a carrier, the palladium concentration in the catalyst is 0.1 to 0.1.
• the inventors have found that by controlling the concentration within the range of 14 ppb by mass, the progress of side reactions can be suppressed, thereby enabling continuous and stable operation for a long period of time, and completed the present invention.
• the present invention relates to the following [1] to [4].
• [1] A method for producing ethyl acetate by reacting ethylene and acetic acid in the presence of a catalyst in which a heteropolyacid or a salt thereof is supported on a carrier, A method for producing ethyl acetate, wherein the palladium concentration in the catalyst is in the range of 0.1 to 14 mass ppb.
• [2] The method for producing ethyl acetate according to [1], wherein the heteropolyacid is silicotungstic acid or phosphotungstic acid.
• [3] The method for producing ethyl acetate according to [1] or [2], wherein the carrier is silica.
• a method for producing ethyl acetate in which ethylene and acetic acid are reacted and which suppresses the progress of side reactions and enables continuous and stable operation for a long period of time. can be done.
• a method for producing ethyl acetate is a method for producing ethyl acetate by reacting ethylene and acetic acid in the presence of a catalyst in which a heteropolyacid or a salt thereof is supported on a carrier, and comprising a specific palladium concentration
• ethyl acetate is produced by reacting ethylene and acetic acid in the gas phase using a solid acid catalyst.
• a solid acid catalyst for producing ethyl acetate contains a heteropolyacid or a salt thereof (also referred to as a "heteropolyacid salt" in the present disclosure) as a main active component of the catalyst, and the heteropolyacid or a salt thereof is supported on a carrier. things are used.
• a heteropolyacid or a salt thereof supported on a carrier is simply referred to as a "catalyst.”
• Heteropolyacid and its salt A heteropolyacid is an acid composed of a central element and peripheral elements to which oxygen is bonded.
• the central element is usually silicon or phosphorus, but can be selected from any one of the many elements of Groups 1-17 of the Periodic Table of the Elements.
• Examples of the central element constituting the heteropolyacid include cupric ions; divalent ions of beryllium, zinc, cobalt, or nickel; trivalent ions of boron, aluminum, gallium, iron, cerium, arsenic, antimony, Ions of phosphorus, bismuth, chromium, or rhodium; ions of tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, platinum, thorium, hafnium, cerium, and other rare earth ions pentavalent phosphorus, arsenic, vanadium, antimony ions; hexavalent tellurium ions; and heptavalent iodine ions, but are not limited to these.
• peripheral elements include, but are not limited to, tungsten, molybdenum, vanadium, niobium, and tantalum.
• heteropolyacids are known as “polyoxoanions”, “polyoxometal salts", or “metal oxide clusters”.
• Some structures of well-known anions are named after researchers in the field, e.g., Keggin-type structures, Wells-Dawson type structures, and Anderson-Evans-Perloff type structures are known.
• Keggin-type structures e.g., Keggin-type structures
• Wells-Dawson type structures e.g., and Anderson-Evans-Perloff type structures are known.
• Heteropolyacids are usually of high molecular weight, eg, having a molecular weight in the range of 700-8500, and include not only their monomers but also dimer complexes.
• the heteropolyacid salt is not particularly limited as long as it is a metal salt or onium salt in which some or all of the hydrogen atoms of the above heteropolyacid are substituted.
• Examples include, but are not limited to, metal salts of lithium, sodium, potassium, cesium, magnesium, barium, copper, silver, and gallium, and onium salts such as ammonium salts.
• Heteropolyacids that can be used as catalysts include, but are not limited to, the following. Silicotungstic acid H 4 [SiW 12 O 40 ].xH 2 O Phosphotungstic acid H 3 [PW 12 O 40 ].xH 2 O Phosphomolybdic acid H 3 [PMo 12 O 40 ].xH 2 O Silicomolybdate H4 [ SiMo12O40 ] .xH2O Sivanadotungstic acid H 4+n [SiV n W 12-n O 40 ].xH 2 O Phosphorvanadotungstic acid H 3+n [PV n W 12-n O 40 ].xH 2 O Phosphovanadomolybdate H 3+n [PV n Mo 12-n O 40 ].xH 2 O Sivanadomolybdate H 4+n [SiV n Mo 12-n O 40 ].xH 2 O Silicomolybdotungstic acid H 4 [SiMo n W 12-n O 40 ].x
• the heteropolyacid is preferably silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silivanadotungstic acid, or phosphovanadotungstic acid, and more preferably silicotungstic acid or phosphotungstic acid.
• a heteropolyacid can be obtained by heating an acidic aqueous solution (about pH 1 to pH 2) containing a salt of molybdic acid or tungstic acid and a heteroatom simple oxygen acid or a salt thereof.
• the heteropolyacid compound can be isolated, for example, by crystallization and separation as a metal salt from the produced heteropolyacid aqueous solution.
• heteropolyacids A specific example of the production of heteropolyacids is described in 1413 of "New Experimental Chemistry Course 8 Synthesis of Inorganic Compounds (III)" (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., August 20, 1984, 3rd edition). page, but is not limited to this.
• the structure of the synthesized heteropolyacid can be confirmed by X-ray diffraction, UV or IR spectrum measurement as well as chemical analysis.
• heteropolyacid salts include lithium, sodium, potassium, cesium, magnesium, barium, copper, silver, gallium, and ammonium salts of the above preferred heteropolyacids.
• heteropolyacid salts include lithium silicotungstic acid, sodium silicotungstic acid, cesium silicotungstic acid, copper silicotungstic acid, silver silicotungstic acid, and gallium silicotungstic acid.
• phosphotungstic acid lithium salt phosphotungstic acid sodium salt, phosphotungstic acid cesium salt, phosphotungstic acid copper salt, phosphotungstic acid silver salt, phosphotungstic acid gallium salt;
• heteropolyacid salts include lithium silicotungstic acid, sodium silicotungstic acid, cesium silicotungstic acid, copper silicotungstic acid, silver silicotungstic acid, gallium silicotungstic acid; Lithium salts of acids, sodium salts of phosphotungstic acid, cesium salts of phosphotungstic acid, copper salts of phosphotungstic acid, silver salts of phosphotungstic acid, gallium salts of phosphotungstic acid; lithium salts of phosphomolybdic acid, phosphomolybdic acid sodium salt of phosphomolybdate, cesium phosphomolybdate, copper phosphomolybdate, silver phosphomolybdate, gallium phosphomolybdate; lithium silicomolybdate, sodium silicomolybdate, silicomolybdate Cesium salts, copper salts of silicomolybdate, silver salts of silicomolybdate, gallium salts of silicomolybdate; lithium silicovanado
• heteropolyacid salt a lithium salt of silicotungstic acid or a cesium salt of phosphotungstic acid is particularly suitable.
• the carrier is not particularly limited, and porous substances generally used as catalyst carriers can be used.
• Preferred supports include, for example, silica, alumina, silica-alumina, diatomaceous earth, montmorillonite, titania, and zirconia, more preferably silica.
• the carrier preferably has a specific surface area of 10 to 1000 m 2 /g, more preferably 100 to 500 m 2 /g, as measured by the BET method.
• the bulk density of the carrier is preferably in the range of 50-1000 g/L, more preferably in the range of 300-500 g/L.
• the bulk density of the carrier is measured by adding the carrier into a graduated glass cylinder in several batches and tapping the graduated cylinder containing the carrier each time until the measured volume of the graduated cylinder becomes exactly the same. It is a value calculated from the weight of the carrier and the volume of the graduated cylinder after charging the carrier.
• the water absorption rate of the carrier is preferably 0.05-3 g-water/g-carrier, more preferably 0.1-2 g-water/g-carrier.
• the average pore diameter is preferably in the range of 1 to 1000 nm, more preferably in the range of 2 to 800 nm.
• the average pore diameter is 1 nm or more, diffusion of gas can be facilitated.
• the average pore diameter is 1000 nm or less, the specific surface area of the carrier necessary for obtaining catalytic activity can be ensured.
• the shape of the carrier There are no particular restrictions on the shape of the carrier. Examples include powder, spherical, and pellet shapes. An optimum shape can be selected according to the reaction type, reactor, etc. used.
• the carrier particles there are no particular restrictions on the size of the carrier particles.
• the carrier is spherical, its particle diameter is preferably in the range of 1-10 mm, more preferably in the range of 2-8 mm. If the particle diameter is 1 mm or more when the reaction tube is filled with the catalyst and the reaction is carried out, an excessive increase in pressure loss when the gas is circulated can be prevented, and the gas can be effectively circulated. When the particle diameter is 10 mm or less, the source gas can be easily diffused into the interior of the catalyst, and the catalytic reaction can proceed effectively.
• a method for supporting a heteropolyacid or a salt thereof on a carrier includes a step of absorbing (impregnating) an aqueous solution of the heteropolyacid or a salt thereof (aqueous heteropolyacid solution) into the carrier (impregnation step), and impregnating the carrier with the aqueous heteropolyacid solution. a step (drying step) of drying the dried carrier under specific drying conditions (drying step) in this order. Between the impregnation step and the drying step, other steps (for example, an air drying step, a transfer step from the impregnation device to the drying device, etc.) may be included, but these two steps are preferably performed continuously. .
• the form of palladium contained in the catalyst is not particularly limited, and examples thereof include metallic palladium, palladium oxide, inorganic salts of palladium, and palladium complexes. Palladium may be unintentionally mixed in during catalyst preparation. For example, this is the case when the catalyst of one embodiment is prepared using the same apparatus after the catalyst using palladium is manufactured.
• the concentration of palladium contained in the catalyst is in the range of 0.1 to 14 mass ppb, preferably in the range of 0.5 to 12 mass ppb, and in the range of 1 to 10 mass ppb. is more preferable. If the palladium concentration exceeds 14 ppb by mass, the catalyst may deteriorate due to side reactions.
• the concentration is based on the mass of the entire catalyst including the heteropolyacid or its salt and the carrier.
• the catalyst As a quantitative analysis method for ppb level palladium contained in the catalyst, the catalyst is calcined in an oxidizing atmosphere, then palladium is extracted from the obtained calcined body into an acidic solution, and the noble metal concentration in the obtained extract is determined.
• a method of measuring by ICP mass spectrometry can be mentioned. Specifically, the analytical procedure described in the section of Comparative Catalyst F used in Comparative Examples below is used.
• ethyl acetate can be obtained by reacting acetic acid and ethylene in the gas phase using a heteropolyacid supported on a carrier or a salt thereof as a solid acid catalyst.
• the method for producing ethyl acetate preferably includes the step of measuring the concentration of palladium in the catalyst before the reaction of acetic acid and ethylene, and the reaction includes a concentration of palladium of 0.1 to Catalysts in the range of 14 mass ppb are used.
• Acetic acid and ethylene are preferably diluted with an inert gas such as nitrogen gas in terms of removing reaction heat.
• an inert gas such as nitrogen gas
• a gas containing acetic acid and ethylene, which are raw materials, is passed through a container filled with a solid acid catalyst and brought into contact with the solid acid catalyst, thereby allowing them to react.
• the reaction is carried out in the presence of water vapor.
• the amount of water added is preferably 0.5 to 15 mol %, more preferably 2 to 8 mol %, as a molar ratio of water to the sum of acetic acid, ethylene and water.
• the ratio of ethylene and acetic acid used as raw materials is not particularly limited. A range of 20:1 is more preferred, and a range of 5:1 to 15:1 is even more preferred.
• the reaction temperature is preferably in the range of 50°C to 300°C, more preferably in the range of 140°C to 250°C.
• the reaction pressure is preferably in the range of 0 PaG to 3 MPaG (gauge pressure), more preferably in the range of 0.1 MPaG to 2 MPaG (gauge pressure). In one embodiment, the reaction temperature is 150-170° C. and the reaction pressure is 0.1-2.0 MPaG (gauge pressure).
• aqueous solution was added to 0.3 L (134 g) of a commercially available silica carrier (spherical, diameter: about 5 mm, bulk density: 451 g / L), and the carrier was thoroughly stirred to impregnate the silicotungstic acid. It was supported on a silica carrier.
• the silica carrier supporting silicotungstic acid was transferred to a porcelain dish, air-dried for 1 hour, and then placed in a ventilated box-type hot-air dryer (experimental ventilation rack Drying was performed for 1 hour with a type dryer, model name: LABO-4CS, Nagato Electric Works Co., Ltd.) to obtain catalyst A (Pd concentration calculated from charge: 5 mass ppb).
• Catalyst B (Pd concentration calculated from charge: 7 mass ppb) was obtained in the same manner as Catalyst A, except that the amount of palladium nitrate used was changed to 0.004 mg.
• Comparative catalyst C (Pd concentration calculated from charge: 15 mass ppb) was obtained in the same manner as catalyst A, except that the amount of palladium nitrate used was changed to 0.008 mg.
• Comparative catalyst D (Pd concentration calculated from charge: 25 mass ppb) was obtained in the same manner as catalyst A except that the amount of palladium nitrate used was changed to 0.014 mg.
• Reference catalyst E (Pd concentration calculated from charge: 0 mass ppb) was obtained in the same manner as catalyst A except that palladium nitrate was not used.
• [Comparative catalyst F] Commercially available Keggin-type silicotungstic acid 24-hydrate (H 4 SiW 12 O 40 24H 2 O, Nippon Inorganic Chemical Industry Co., Ltd.) and a commercially available silica carrier (spherical, diameter: about 5 mm, bulk density: 451 g/L ) was the same as that of catalyst E in which palladium nitrate was not used, about 300 kg of catalyst F was produced in an actual plant. When the palladium concentration in catalyst F was measured, it was 23 mass ppb. It is presumed that a very small amount of palladium component was mixed for some reason in the manufacturing process of catalyst F. Palladium concentration was measured by the following method.
• 0.1 g of the calcined sample was placed in a quartz beaker, then 3 mL of ultrapure water, 68% by mass nitric acid aqueous solution (HNO 3 ; Tama Chemical Industry Co., Ltd., TAMAPURE-AA-100) 1 mL, and 30% by mass hydrochloric acid (HCl; Tama Kagaku Kogyo Co., Ltd., TMAPURE-AA-100) 1 mL was added.
• the contents were heated on a hot plate set at 100° C. for 2 hours with occasional shaking. After cooling the contents, 5 mL of ultrapure water was added. Subsequently, the solution was filtered through a 0.45 ⁇ m disposable filter and collected in a polypropylene container.
• the quartz beaker was washed with 10 mL of ultrapure water, the washing liquid was filtered through a 0.45 ⁇ m disposable filter, and the filtrate was collected in a polypropylene container. The washing operation was performed 3 times in
• the volume of the filtrate collected in a polypropylene container was adjusted to 50 mL, and the palladium concentration in the solution was quantified by ICP mass spectrometry.
• the palladium concentration (mass ppb) in the comparative catalyst F was calculated from the analytical value of the palladium concentration and the mass of the charged comparative catalyst F.
• the reaction was carried out by adjusting the reaction temperature so that the highest temperature among the 10 parts of the catalyst layer was 165.0°C.
• the gas that passed through for a predetermined time from the start of the reaction was condensed with cooling water and collected (hereinafter referred to as "condensate"), and the obtained condensate was analyzed.
• the uncondensed gas remaining without condensation (hereinafter referred to as "uncondensed gas”) was measured for the same amount of time as the condensed liquid, and 100 mL of the gas was taken out for analysis.
• Condensate analysis method The condensate was analyzed with a gas chromatograph. Using the internal standard method, 1 mL of 1,4-dioxane was added as an internal standard to 10 mL of the reaction solution, and 0.2 ⁇ L of the solution was added to analyze under the following conditions.
• Uncondensed gas was analyzed by a gas chromatograph. Using the absolute calibration curve method, 100 mL of uncondensed gas was sampled, and the entire amount of this was flowed into a 500 ⁇ L gas sampler attached to the gas chromatography apparatus, and analyzed under the following conditions.
• Example 1 40 mL of the catalyst A was filled in the stainless steel reaction tube (gas-phase flow reactor), and the synthesis reaction of ethyl acetate was carried out. After 5 hours and 200 hours of reaction, the condensed liquid and uncondensed gas were analyzed, and the ethyl acetate space-time yield and butene selectivity were calculated. Table 1 shows the results.
• Example 2 Ethyl acetate was synthesized and analyzed in the same manner as in Example 1 except that catalyst B was used instead of catalyst A. Table 1 shows the results.
• Catalyst F of Comparative Example 3 had a palladium concentration of 23 mass ppb. Compared to Reference Catalyst E, Comparative Catalyst F has a higher selectivity for by-product butene.
• the concentration of palladium in the manufactured catalyst can be confirmed to ensure the production of ethyl acetate. can be determined prior to use in the actual plant. As a result, it becomes possible to increase the production efficiency of ethyl acetate in an actual plant.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86774356

Family Applications (1)

Country Status (6)

Citations (5)

Family Cites Families (2)

• 2022
  • 2022-10-24 CN CN202280081551.8A patent/CN118369307A/zh active Pending
  • 2022-10-24 WO PCT/JP2022/039570 patent/WO2023112488A1/ja not_active Ceased
  • 2022-10-24 JP JP2023567579A patent/JP7685138B2/ja active Active
  • 2022-10-24 GB GB2407646.5A patent/GB2627636A/en active Pending
  • 2022-10-24 US US18/694,549 patent/US20250002441A1/en active Pending
  • 2022-11-03 TW TW111141955A patent/TWI833417B/zh active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events