CN102892742B - Purification of carboxylic acids by catalytic hydrogenation - Google Patents
Purification of carboxylic acids by catalytic hydrogenation Download PDFInfo
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- CN102892742B CN102892742B CN201180009759.0A CN201180009759A CN102892742B CN 102892742 B CN102892742 B CN 102892742B CN 201180009759 A CN201180009759 A CN 201180009759A CN 102892742 B CN102892742 B CN 102892742B
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- 238000000746 purification Methods 0.000 title claims abstract description 84
- 150000001735 carboxylic acids Chemical class 0.000 title abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000002253 acid Substances 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- -1 bottle Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000011027 product recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000015073 liquid stocks Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Classifications
-
- 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/0061—Controlling the level
Abstract
The present invention relates to a process for the production of an aromatic carboxylic acid comprising: a) introducing a crude aromatic carboxylic acid solution into a purification reactor vessel, wherein the purification reactor vessel is operating under pressure, b) introducing hydrogen gas into the purification reactor vessel, c) dissolving the hydrogen gas in the crude aromatic polycarboxylic acid solution as the solution flows down a wall of a vertical conduit onto a distributor, wherein the purification reactor vessel has a gas-liquid contact area to plant throughput (capacity) ratio of at least 0.55 m2/ te/h of carboxylic acid for dissolving the hydrogen gas in the crude aromatic polycarboxylic acid solution to produce a reaction solution, and d) contacting the reaction solution with a supported catalyst bed to produce a purified aromatic carboxylic acid,; wherein the supported catalyst bed is submerged in the reaction solution and a liquid level of the reaction solution is maintained above the supported catalyst bed.
Description
the cross reference of related application
The application requires the rights and interests of the right of priority of the U.S. Provisional Application number 61/304567 of submitting on February 15th, 2010.
Invention field
The present invention relates to the method for purifying aromatic polycarboxylic acid, and be particularly related to the catalytic hydrogenation reaction for the preparation of the aromatic polycarboxylic acid of purifying.
background of invention
Aromatic polycarboxylic acid is commercially important chemical intermediate, and particularly as polyester raw material, it is for the manufacture of fiber, bottle, film and electronic application.
Aromatic polycarboxylic acid, for example terephthalic acid, the preparation of m-phthalic acid and naphthalic acid, generally includes oxidation step and purification step subsequently.This oxidation step comprises a kind of method, wherein such as dimethylbenzene of polyoxyethylene alkyl aryl family hydrocarbon precursor, trialkyl benzene or dialkyl group naphthalene, at high temperature and high pressure and heavy metal under for example cobalt, manganese and bromine compounds exist, in aqueous acetic acid solvent by molecular oxygen oxidation.In the thick aromatic polycarboxylic acid obtaining by above-mentioned oxidizing reaction, comprise such as the impurity such as monocarboxylic acid and aldehyde, they are intermediate products of oxidizing reaction, bromine adducts and derive from the metal component of catalyzer, and there is the coloring material of unknown structure.Be enough to and the purification step of glycol direct esterification with the aromatic polycarboxylic acid of the purity of production polyester polymers for the production of having, relate to a kind of method, wherein thick aromatic polycarboxylic acid for example, in High Temperature High Pressure with under catalyzer (the VIII group 4 transition metal on carbon support) exists, in the water as solvent, be hydrogenated, for example, as U.S. Patent number 3, disclosed in 584,039.Purifying aromatic polycarboxylic acid after hydrogenation reaction can be directly used in to be produced polymkeric substance or conventionally adopt and makes with the following method itself and separated from solvent: make aromatic polycarboxylic acid crystallization, crystallized product is separated and be dried to obtain dry crystallized product with water solvent.
summary of the invention
The problem of traditional method purifying aromatic polycarboxylic acid comprises: i) for dissolving aromatic polycarboxylic acid and holding the required number of containers of working liquid stock (inventory) of solution, and ii) for dissolving hydrogen, the liquid that makes to contain thick aromatic polycarboxylic acid contacts with catalyzer with hydrogen and provides enough residence time to complete the reactor size of purification reaction.Conventionally,, because the solubleness of hydrogen in aromatic polycarboxylic acid solution is limited, need to maintain high reactor pressure and be dissolved in to ensure sufficient hydrogen the purifying that completes thick aromatic polycarboxylic acid in aqueous solvent.Another one problem is the shortening of the catalyzer operation life due to solid support material destroys, and it results from and in purification reaction, uses heterogeneous catalyst.
The consequence of these combinatorial problems, or be because equipment cost is higher or catalyst life reduces the running cost increase causing, or be that the purified product that poor operation control brings changes larger.
One object of the present invention is reduce or avoid one or more in the problems referred to above.Particularly, an object of the present invention is to provide improved continuation method, it is for contacting with supported catalyst under high temperature and high pressure, with the hydrogen purification aromatic polycarboxylic acid aqueous solution.Have been found that a kind of method of carrying out purification reaction, it comprises from the reaction intermediate of aromatic aldehyde and is converted into corresponding one dollar aromatic carboxylic acid.The present invention relates to the method for the production of aromatic carboxylic acid, comprise: a) thick aromatic carboxylic acid's solution is incorporated in purification reaction container, wherein this purification reaction container operates under pressure, b) hydrogen is introduced in this purification reaction container, c) in the time that solution flows on divider downwards along vertical ducting wall, hydrogen is dissolved in thick aromatic polycarboxylic acid solution, and wherein the ratio of the gas-to-liquid contact area of this purification reaction container and device processes amount (plant throughput) (capacity) is at least 0.55 m
2/ te/h carboxylic acid, it is processed for hydrogen being dissolved in to thick aromatic polycarboxylic acid solution to produce reaction soln, and d) reaction soln is contacted with supported catalyst bed, produce the aromatic carboxylic acid of purifying, wherein supported catalyst bed is immersed in reaction solution, and keeps the liquid level of reaction solution higher than supported catalyst bed.This catalyst bed is completely submerged, and the thick polycarboxylic acid dissolving (slightly acid) solution level remains on supported catalyst.The benefit of this working method is by guaranteeing that gaseous hydrogen does not directly contact to extend the operation life of supported catalyst bed with the granules of catalyst of load, and by keep thick acid solution level stability higher than supported catalyst bed to reduce the variation of product quality.Another object of the present invention is in the time that hydrogen enters purification reactor, improve its solvability in thick acid solution by increasing the liquid surface area contacting with gaseous hydrogen, with the reduction quick variation of working pressure and the fluctuation of purification reactor liquid level, and this fluctuation causes the variation of polycarboxylic acid (purifying acid) the product quality of purifying.Another object is to reduce the quantity of container and the total residence time of aromatic carboxylic acid's solution, thereby significantly reduces the required equipment cost of purification step in manufacturing processed.
accompanying drawing summary
Fig. 1 illustrates one embodiment of the invention schematic diagram of (having shown purification reactor).
Fig. 2 illustrates one embodiment of the invention schematic diagram of (having shown liquid dispenser).
Fig. 3 is the schematic diagram of conventional purification reactor.
describe in detail
The present invention relates to the method for the production of aromatic carboxylic acid, comprise: a) thick aromatic carboxylic acid's solution is incorporated in purification reaction container, wherein this purification reaction container operates under pressure, b) hydrogen is incorporated in this purification reaction container, c) in the time that solution flows on divider downwards along vertical ducting wall, hydrogen is dissolved in thick aromatic polycarboxylic acid solution, and wherein the ratio of the gas-to-liquid contact area of this purification reaction container and device processes amount (capacity) is at least 0.55 m
2/ te/h carboxylic acid, hydrogen is dissolved in thick aromatic polycarboxylic acid solution to produce reaction soln, and d) by tactile to reaction soln and supported catalyst bench grafting, produce the aromatic carboxylic acid of purifying, wherein supported catalyst bed is immersed in reaction solution, and keeps the liquid level of reaction solution higher than supported catalyst bed.The ratio of the gas-to-liquid contact area in step c) and device processes amount (capacity) can be approximately 0.65 m
2/ te/h carboxylic acid or more, for example about 0.75m
2/ te/h carboxylic acid or more, or 1.2m
2/ te/h carboxylic acid or more.Divider can comprise that i) diameter is approximately 0.3 to approximately 0.7 perforated disc (circular disc) of purification reaction container diameter, II) around the notched weir opening (notched weir openings) of edge placement of dish (plate), so that thick acid solution is remained on dish; And III) at least one hole, reaction soln flows on the fluid surface of divider below through it.Divider also can comprise that i) diameter is approximately 0.3 to approximately 0.7 perforation annular open tube or groove (channel) of purification reaction container diameter, II) the notched weir opening arranged around pipe or groove edge, so that thick acid solution is remained on dish; And III) at least one hole, reaction soln flows on the fluid surface of divider below through it.Divider can be positioned at the position higher than 0.5 to 2 meter of thick acid solution liquid level, and for example 0.5 to 1.0 meter, and flow through this hole cross notched weir opening of thick acid solution.Optionally, can use alternative liquid dispenser configuration with flow to catalyst bed top when thick acid solution and keep liquid volume time the liquid surface area contacting with gas phase of increase is provided.Aromatic polycarboxylic acid can be terephthalic acid.
One embodiment of the invention comprise dissolving part (dissolution section) bottom that by entrance, thick acid solution is fed to purification reactor, wherein all thick acid solutions are along the flow path of extending, overflow to the vertical ducting of plate distributor top, and on the gas-to-liquid contact area of purification reactor, (comprise dissolver or dissolve part) that stop exceedes the minimum residence time (approximately 3.0 minutes or longer).For example, can be approximately 3.5 minutes or longer in the minimum residence time of dissolving part, or approximately 4.0 minutes or longer.Can be approximately 3.5 minutes or longer in the minimum residence time of dissolving part and the total of the liquid level above catalyzer, or 4.0 minutes or longer.The configuration of inlet tube comprises bend pipe, the opening of aligning or other device that becomes known for draining into dissolver or dissolve part.
In another embodiment, extra liquid dispenser is positioned at the top of downtake, to make liquid to spray providing extra Surface Contact area downwards along the inside of downtake.In this case, liquid dispenser can be pipe or groove (trough), its orientation of top across downtake, the substrate of each groove or pipe has multiple holes, liquid flows into groove or pipe by this, these holes of then flowing through, and this produces liquid spray effectively in downtake.
Another embodiment of the invention relates to the control of the gaseous tension in thick acid solution liquid level and purification reactor.The control of these two parameters comprise by regulate maintain gaseous tension in the setting pressure of approximately 0.5 bar from the flow velocity of purification reactor purifying acid solution out.Change in flow is restricted to maintain the minimum liquid level of catalyst bed top, and this is in-50% to+100% scope of normal flow conventionally.In this way, Controlling System keeps stable liquid level and purification reactor pressure.The flow hydrogen gas that also can enter purification reactor by adjusting is controlled liquid level.The present invention can be described to further comprise that step e) is by regulating the reaction soln liquid level of controlling supported catalyst bed top reactor pressure and purification reaction container from purification reaction container liquid-flow out; Or e) by regulating the reaction soln liquid level of controlling supported catalyst bed top reactor pressure and purification reaction container from purification reaction container liquid-flow out and the flow hydrogen gas that enters purification reaction container; Or e) enter purification reaction container by adjusting flow hydrogen gas control the reaction soln liquid level of supported catalyst bed top in reactor pressure and purification reaction container, wherein the hydrogen pressure in purification reaction container is greater than 60barA.
Another embodiment of the invention can be wherein step a) and is further included in and enters before purification reaction container, thick aromatic polycarboxylic acid solution is heated to the temperature within the scope of approximately 275 DEG C to approximately 291 DEG C, for example, entering 280 ° of C of purification reaction container precontract to approximately 289 DEG C, or than the temperature that thick aromatic polycarboxylic acid is dissolved in at least 3 DEG C of temperature height required in water.
All embodiments of the present invention may further include following content.Purification reactor comprises four parts: part is dissolved on top; Downtake and distribution plate; The liquid volume of controlling, it is located immediately at last part, i.e. the top of supported catalyst bed it is flooded completely.The depth-width ratio of purification reactor, is defined as the ratio of the length of container column part and the diameter of catalyst bed, and approximately 2 to approximately 4.5, for example approximately 3 to approximately 3.5 scope.The hydrogen that is fed to purification reactor comprises that approximately 90% v/v arrives the hydrogen within the scope of approximately 99.9% v/v to approximately 99.9% v/v, particularly approximately 95% v/v.The gas that is fed to purification reactor can comprise condensable component or the inert component of not reacting with thick acid or supported catalyst.The gas temperature that is fed to purification reactor can be approximately 40 DEG C to approximately 290 ° C.This gas is the gas of supercharging, enters the front pressure at least 70 bar of purification reactor, and conventionally than the high 1-5 bar of the air pressure in purification reactor, can accurately control the gaseous tension of purification reactor inside.Hydrogen can be used as the hydrogen source in the inventive method, combines with catalyzer, makes the impurity hydrogenation in thick acid.Before touching with supported catalyst bench grafting, hydrogen/thick acid solution (reaction soln) is even liquid phase.
Reactor of the present invention is continuous flow reactor." continuous flow reactor " used herein, is defined as such reactor, wherein in a continuous manner introducing simultaneously and mixed reactant and discharge product, this is contrary with batch reactor.Although a kind of suitable configuration of purification reactor is the vertical cylindrical vessel with constant diameter, each part of purification reactor can have different diameters.
The free volume that reaction times is defined as in catalyst bed is passed through the corresponding time of volumetric flow rate of catalyst bed divided by reaction soln, can control this reaction times makes thick polycarboxylic acid can be converted into efficiently the polycarboxylic acid of purifying, to comprise and be no more than about 25ppm at the polycarboxylic acid that completes the purifying being precipitated out after purification reaction from reaction medium, the intermediate of the conduct that is for example no more than about 15ppm in oxidising process and the aldehyde (for example 4-CBA in Production of Terephthalic Acid) that produces.Conventionally, after reaction, will there are at least some aldehyde, and be generally at least 5ppm.Similarly, the aldehyde intermediate producing in oxidation reaction process can be converted into corresponding monobasic aromatic carboxylic acid (for example in Production of Terephthalic Acid to toluic acid) efficiently, for example, to comprise and be no more than about 200ppm completing the purifying acid being precipitated out after purification reaction from reaction medium, be no more than the monobasic aromatic carboxylic acid of about 150ppm.Conventionally, after reaction, will there are at least some monobasic aromatic carboxylic acids, and be generally at least 140 ppm.
With reference to Fig. 1 and 2, the present invention may be better understood.Comprise that Fig. 3 is to compare with the present invention.
With reference to figure 1, the incoming flow 1 that enters purification reactor project A can be included in as the thick acid solution of the heating in the water of solvent.The composition of incoming flow 1 can comprise the thick acid/water of 20%w/w-35%w/w, for example 27%w/w-33%w/w.Incoming flow 1 can, from slurry mix tank, be heated slurry to dissolve thick acid by preheater.Incoming flow 1 is heated to the temperature within the scope of approximately 275 DEG C to approximately 291 DEG C, for example approximately 280 DEG C to approximately 289 DEG C.Depending in the required temperature in this position that needs obtain exceeds the carboxylic acid temperature required limit of temperature (margin) that is dissolved in the water.Conventionally use 3-10 DEG C, for example limit of temperature of 4-7 DEG C.Incoming flow 1 is fed to purification reactor project A by entrance project B.The outlet of entrance project B is positioned at and approaches the bottom of dissolving some projects C.In the time that the inlet tube B of this configuration leans against purification reaction container textural, Fig. 1 shows the downtake project D as the tube axial in container cross section central authorities.An embodiment comprises the dissolver part that is constructed to cylinder sealed can and the cup dolly with the second cylinder, the second cylinder also with purification reaction container co-axial orientation,, and be connected with distribution tray project E at its bottom opening place as downtake at purification reaction container upper section.Downtake can form pipe or ring.
The outlet of entrance project B is near the bottom of dissolver some projects C, to guarantee that the residence time of all thick acid in dissolver some projects C exceedes the minimum time length within the scope of approximately 3 minutes to approximately 10 minutes, for example approximately 3.5 minutes to approximately 5.5 minutes, and guarantee not have cycling stream obstruction (short-circuit) to overflow to the flowing-path downtake from entrance.The advantage of this configuration is the solid of guaranteeing in any water insoluble solvent, is flowing through after preheater, and entering before purification reactor entrance, in dissolver part, stopping enough time length dissolves completely, to avoid blocking catalyst bed.
Thick acid solution, from the dissolver some projects C downtake project D that flows through, arrives the divider project E shown in Fig. 2 downwards.Divider project E collects thick acid solution, makes its distributed uniform, and now it continues to flow to the next section of purification reactor, and increases the surface-area of liquid, is beneficial to improve the solubleness of hydrogen in thick acid solution.Fig. 2 shows circular divider project E, comprises and has the perforation pallet (formation substrate) in multiple holes and have multiple around the divider vertical edge of the otch of interval setting (space) around.
The thick acid solution that comprises dissolved hydrogen flows to the surface of the liquor capacity that is retained in supported catalyst bed project F top as many independently flow (flow stream) from divider project E.The degree of depth of liquid volume is measured by liquid level instrument, for example nucleometer of described liquid level instrument (nucleonic gauge), can be from Tracerco, Johnson Mttehey plc, Pavilion 11, Belasis Hall Technology Park, Coxwold Way, Billingham, Cleveland TS23 4EA obtains; Buoy; Conducting probe or other suitable instrument.The hydrogen stream that also can enter container by adjustment by the severity control of thick acid solution volume to the level of setting.The degree of depth of thick acid solution volume is for example, higher than approximately 0.5 meter to approximately 2.0 meters of catalyst bed project F upper surface, in the scope of approximately 0.8 meter to approximately 1.5 meters.The liquid flow rate that flows out purification reactor by adjusting is strictly controlled reaction pressure.Two controllers are set to keep the variation of purification reactor internal pressure to be less than liquid level change, to avoid unsettled interaction between each control loop.
Maintain liquid level higher than catalyst bed project F, the liquid stream of supported catalyst bed project F of having guaranteed to flow through is uniformly distributed, and advantageously reduces thick acid solution by being converted into the volume of the required supported catalyst bed project F of the acid solution of purifying with hydrogen and supported catalyst contact reacts.Fig. 3 shows the conventional purification reactor with Fig. 1 contrast.
Process outside Fig. 1 middle outlet project G can comprise pipe, and purification reactor export project G is connected to flow director by it, for example flowrate control valve, and flow to product crystallization and the recovery part in downstream.Can be by causing in one or more stages or allowing crystallization from solution, then solid-liquid separation and reclaim required product, i.e. the acid of purifying in one or more stages.
The regulation and control stream of the acid solution of purifying can flow to product recovery part, can from solution, be settled out at this carboxylic acid.Can adopt any appropriate method that reclaims product.Product recovery part can comprise the cooling or evaporative crystallization in one or more stages, so that the acid product crystallization of purifying is formed on the crystal slurry in aqueous mother liquor.In the time that product recovery part comprises one or more flash evaporation crystallizer, the flash streams obtaining from crystallizer can be used for indirectly by conventional heat exchanger or directly flash streams is expelled to other stream in preheating manufacturing processed process.The slurry obtaining after crystallization can stand solid-liquid separation process, uses for example at super-atmospheric pressure, under normal atmosphere or subatmospheric condition, operates, and is with or without the filter plant of washing device, and for example Andritz or Bokela or MKK provide.Therefore, solid-liquid separation can be used any device that is applicable to this object to carry out, and is arranged as under the condition of pressure that depends on final crystallisation stage and operates.Solid-liquid separation can use integrated solid to separate and washing equipment carries out, for example band filter unit, rotatable drumfilter unit, or rotary drum filter unit (for example, the BHS-Fest filter drum being formed by multiple chambers (cell) receives slurry, and wherein by being provided to the hydraulic pressure of the water in these chambers, mother liquor is separated from filter cake).After slurries filtration, the carboxylic acid product of recovery can be directly used in production polyester, for example, for example, for packaging, bottle or fiber.Equally also can be dried.If not yet reach normal atmosphere, the filter cake of carboxylic acid product can be transferred to low pressure area (for example normal atmosphere), to be dried by suitable decompression device.
After the acid product of purifying reclaims, at least partly aqueous mother liquor can recirculation to recycle in purge process, for example, by mixing with fresh water and/or reactant.But, in mother liquor, also comprise the valuable reaction intermediate that can be recovered, to improve the products collection efficiency of manufacturing processed.With regard to the manufacture of terephthalic acid, these intermediates comprise P-phenylformic acid and 4-carboxyl benzaldehyde.But, in mother liquor, also contain the material and precursor and reaction and the degradation by-products that form color, and can clean during the course to reduce the residual concentration of these components.Purge flow can be sent to effluent processing, for example aerobic and/or anaerobic treatment or other removal process.
Although main, with reference to the p-Xylol as terephthaldehyde's acid precursor, present invention is described, it should be understood that and also can utilize other precursor replace p-Xylol or except p-Xylol, also can utilize other precursor to produce corresponding carboxylic acid.These precursors comprise such as m-xylene of polyoxyethylene alkyl aryl family hydrocarbon, and trialkyl benzene or dialkyl group naphthalene are respectively used to produce for example m-phthalic acid of aromatic carboxylic acid and naphthalic acid.To further illustrate the present invention by following unrestricted embodiment below.
Embodiment
The following examples comprise from the data of the purification reactor of isomorphism type not.Comparative example has shown the design of popular response device, as disclosed in Fig. 3.Embodiment 1 and 2 is embodiments of purification reactor of the present invention, to show the improvement of catalyst life and catalyst productivity.
comparative examplepopular response device design (Fig. 3)
Reactor diameter 3.145 m
Capacity 53 te/h PTA capacity
Gas-to-liquid contact area 23.4 m
2
Gas-to-liquid contact area: reactor diameter 0.45 m
2/ te/h PTA
Reactor catalyst loading capacity 21 te
Catalyst life 12 months
Catalyst productivity 25,000 te PTA/te catalyzer
embodiment 1
Reactor diameter 3.300 m
Capacity 82 te/h PTA capacity
Dissolver, downtake and divider
In gas-to-liquid contact area 52 m
2
Gas-to-liquid contact area: reactor diameter 0.63 m
2/ te/h PTA
Reactor catalyst loading capacity 20-24 te
Catalyst life 18-24 month
Catalyst productivity 50,000 te PTA/te catalyzer
embodiment 2
Reactor diameter 3.600 m
Capacity 90 te/h PTA capacity
Dissolver, downtake and divider
In gas-to-liquid contact area 67 m
2
Gas-to-liquid contact area: reactor diameter 0.744 m
2/ te/h PTA
Reactor surface area 10.2 m
2
Reactor catalyst loading capacity 24-28 te
Catalyst life 24 months
Catalyst productivity 60,000 te PTA/te catalyzer
Although describe the present invention in conjunction with specific embodiments of the present invention, according to the above description, a lot of replacements, modifications and variations are cheer and bright for those skilled in the art.Therefore, this invention is intended to comprise all this replacement, modifications and variations that fall in claims spirit and scope.
Claims (16)
1. for the production of aromatic carboxylic acid's method, it comprises:
A) thick aromatic carboxylic acid's solution is incorporated in purification reaction container, wherein said purification reaction container operates under pressure,
B) hydrogen is introduced in described purification reaction container,
C) in the time that solution flows on divider downwards along vertical ducting wall, hydrogen is dissolved in thick aromatic polycarboxylic acid solution, the gas-to-liquid contact area of wherein said purification reaction container and the ratio of device processes amount are at least 0.55 m
2/ te/h carboxylic acid, for hydrogen being dissolved in to thick aromatic polycarboxylic acid solution to produce reaction soln, and
D) reaction soln and supported catalyst bench grafting are touched to the aromatic carboxylic acid to produce purifying, wherein said supported catalyst bed is immersed in reaction soln, and keeps the liquid level of reaction soln higher than supported catalyst bed.
2. the process of claim 1 wherein that gas-to-liquid contact area in step c) and the ratio of device processes amount are 0.65 m
2/ te/h carboxylic acid or more.
3. the process of claim 1 wherein that gas-to-liquid contact area in step c) and the ratio of device processes amount are 0.75 m
2/ te/h carboxylic acid or more.
4. the process of claim 1 wherein that gas-to-liquid contact area in step c) and the ratio of device processes amount are 1 m
2/ te/h carboxylic acid or more.
5. the process of claim 1 wherein that described divider comprises that i) diameter is 0.3 to 0.7 perforated disc of purification reactor container diameter, II) around the notched weir opening of the edge placement of dish, so that thick acid solution is remained on dish; And III) at least one hole, thick aromatic polycarboxylic acid solution flow on the fluid surface of divider below through it.
6. the process of claim 1 wherein that described divider comprises that i) diameter is 0.5 to 0.9 perforation annular open tube or groove of purification reaction container diameter, II) around the notched weir opening of the edge placement of ring, so that thick acid solution is remained on dish; And III) at least one hole, thick aromatic polycarboxylic acid solution flow on the fluid surface of divider below through it.
7. the method for claim 5 or 6, above the reaction soln liquid level of wherein said divider on supported catalyst bed between 0.5 meter-2.0 meters.
8. the method for claim 5 or 6, above the reaction soln liquid level of wherein said divider on supported catalyst bed between 0.5 meter-1 meter.
9. the process of claim 1 wherein that the residence time of described solution on gas-to-liquid contact area is 3 minutes or longer.
10. the method for claim 1, further comprises that step e) is by regulating the mobile reaction soln liquid level of controlling supported catalyst bed top reactor pressure and purification reaction container from purification reaction container liquid out.
The method of 11. claims 1, further comprises that step e) is by regulating the mobile reaction soln liquid level of controlling supported catalyst bed top reactor pressure and purification reaction container that flows and enter the hydrogen of purification reaction container from purification reaction container liquid out.
The method of 12. claims 1, further comprise that step e) enters the mobile reaction soln liquid level of controlling supported catalyst bed top in reactor pressure and purification reaction container of the hydrogen of purification reaction container by adjusting, wherein the hydrogen pressure in purification reaction container is greater than 60 barA.
13. the process of claim 1 wherein that step a) is further included in enters before purification reaction container, and thick aromatic polycarboxylic acid solution is heated to the temperature within the scope of 275 DEG C-291 DEG C.
14. the process of claim 1 wherein that step a) is further included in enters before purification reaction container, and thick aromatic polycarboxylic acid solution is heated to the temperature within the scope of 280 DEG C-289 DEG C.
15. the process of claim 1 wherein that step a) further comprises is heated to thick aromatic polycarboxylic acid solution than the temperature that thick aromatic polycarboxylic acid is dissolved in at least 3 DEG C of temperature height required in water.
16. the process of claim 1 wherein that described aromatic polycarboxylic acid is terephthalic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30456710P | 2010-02-15 | 2010-02-15 | |
| US61/304,567 | 2010-02-15 | ||
| PCT/US2011/024746 WO2011100682A2 (en) | 2010-02-15 | 2011-02-14 | Purification of carboxylic acids by catalytic hydrogenation |
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| GB201219983D0 (en) * | 2012-11-06 | 2012-12-19 | Davy Process Techn Ltd | Apparatus and process |
| BR112016015320A2 (en) | 2013-12-30 | 2017-10-10 | Bp Corp North America Inc | feed mixtures of pressurized raw aromatic carboxylic acid |
Citations (7)
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|---|---|---|---|---|
| US3546285A (en) * | 1967-06-20 | 1970-12-08 | Celanese Corp | Process of purifying aromatic dicarboxylic acids |
| US3639465A (en) * | 1968-06-18 | 1972-02-01 | Standard Oil Co | Purification of aromatic polycarboxylic acids by catalytic reduction using prehumidified hydrogen |
| CN86106988A (en) * | 1985-10-07 | 1987-04-08 | 阿莫科公司 | Reduce the purification process of 4-carboxyl benzaldehyde content in the terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1396901A (en) * | 2000-02-03 | 2003-02-12 | Bp北美公司 | Low temp. purification of naphthalene dicarboxylic acids |
| CN101115705A (en) * | 2004-12-13 | 2008-01-30 | Bp北美公司 | Process for purification of aromatic carboxylic acids |
| CN101146756A (en) * | 2005-03-21 | 2008-03-19 | Bp北美公司 | Process and apparatus for manufacturing pure forms of aromatic carboxylic acids |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7959879B2 (en) * | 2004-09-02 | 2011-06-14 | Grupo Petrotemex, S.A. De C.V. | Optimized production of aromatic dicarboxylic acids |
-
2011
- 2011-02-14 WO PCT/US2011/024746 patent/WO2011100682A2/en active Application Filing
- 2011-02-14 CN CN201180009759.0A patent/CN102892742B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546285A (en) * | 1967-06-20 | 1970-12-08 | Celanese Corp | Process of purifying aromatic dicarboxylic acids |
| US3639465A (en) * | 1968-06-18 | 1972-02-01 | Standard Oil Co | Purification of aromatic polycarboxylic acids by catalytic reduction using prehumidified hydrogen |
| CN86106988A (en) * | 1985-10-07 | 1987-04-08 | 阿莫科公司 | Reduce the purification process of 4-carboxyl benzaldehyde content in the terephthalic acid |
| CN1036948A (en) * | 1988-03-29 | 1989-11-08 | 阿莫科公司 | The used group VIII noble metals reactivation of catalyst of purified terephthalic crude product method |
| CN1396901A (en) * | 2000-02-03 | 2003-02-12 | Bp北美公司 | Low temp. purification of naphthalene dicarboxylic acids |
| CN101115705A (en) * | 2004-12-13 | 2008-01-30 | Bp北美公司 | Process for purification of aromatic carboxylic acids |
| CN101146756A (en) * | 2005-03-21 | 2008-03-19 | Bp北美公司 | Process and apparatus for manufacturing pure forms of aromatic carboxylic acids |
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|---|---|
| CN102892742A (en) | 2013-01-23 |
| WO2011100682A2 (en) | 2011-08-18 |
| WO2011100682A3 (en) | 2011-12-15 |
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