EP3445483A1 - Verfahren zur durchführung einer heterogen-katalysierten reaktion - Google Patents
Verfahren zur durchführung einer heterogen-katalysierten reaktionInfo
- Publication number
- EP3445483A1 EP3445483A1 EP17716925.7A EP17716925A EP3445483A1 EP 3445483 A1 EP3445483 A1 EP 3445483A1 EP 17716925 A EP17716925 A EP 17716925A EP 3445483 A1 EP3445483 A1 EP 3445483A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zone
- reactor
- catalyst
- ratio
- reaction
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 72
- 239000007789 gas Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 23
- 239000011541 reaction mixture Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005192 partition Methods 0.000 claims description 5
- 238000006709 oxidative esterification reaction Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004062 sedimentation Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 239000002638 heterogeneous catalyst Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 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
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/226—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement internally, i.e. the particles rotate within the vessel
-
- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
- B01J8/224—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement
- B01J8/228—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid the particles being subject to a circulatory movement externally, i.e. the particles leaving the vessel and subsequently re-entering it
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00752—Feeding
-
- 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
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00761—Discharging
-
- 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
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00831—Stationary elements
- B01J2208/0084—Stationary elements inside the bed, e.g. baffles
-
- 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
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00823—Mixing elements
- B01J2208/00858—Moving elements
- B01J2208/00867—Moving elements inside the bed, e.g. rotary mixer
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
- B01J2219/00768—Baffles attached to the reactor wall vertical
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/185—Details relating to the spatial orientation of the reactor vertical
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1946—Details relating to the geometry of the reactor round circular or disk-shaped conical
Definitions
- the present invention relates to a novel process for carrying out a heterogeneously catalyzed reaction, in particular in a liquid phase.
- Heterogeneously catalyzed reactions in a liquid phase are extensively described in the literature. These include e.g. the cobalt-catalyzed Fischer-Tropsch synthesis, palladium- and nickel-catalyzed hydrogenation with hydrogen, numerous oxidation reactions.
- slurry reactors are mainly used for heterogeneously catalyzed processes, for which good mixing and low temperature and concentration gradients are advantageous. Especially for strongly exothermic reactions, it is important to dissipate the heat of reaction as well as possible. That's what the reactors are for
- reaction mixture especially well suited with internal or external circulation of the reaction mixture.
- CN 104418309 describes an inner tube slurry reactor for hydrogen peroxide production in a heterogeneously catalyzed hydrogenation reaction of anthraquinone.
- the catalyst concentration used is about 10 g / L ( ⁇ 0.01 kg / kg mixture) and is thus relatively low.
- the flow direction in the inner tube from bottom to top promotes a large proportion of
- WO 2012/152600 describes an ammoximation of cyclohexanone which is carried out with a heterogeneous TS-1 catalyst as a three-phase reaction (gaseous-liquid-solid) becomes. Both the heat transfer and the mass transfer in this process can be significantly improved if a cylindrical inner tube is used. The educts are added at different points. A metered addition takes place under the inner tube (here NH3), one from above (here H2O) and optionally one laterally (here for example cyclohexanone). Filtration takes place with the help of many candle filters with a large total area. These are placed centrally in the reactor height or on the outer edge of the inner tube. The process can be run on the basis of the description for 1 year without interruptions and filter backwashing. After one year the filters have to be cleaned.
- CN 101314120 describes a loop-slurry reactor with external circulation of the
- the method should allow for the use of readily polymerizable educts and formation of such products and / or by-products such a reactor design that this allows only a very low polymerization at most.
- the method should be inexpensive compared to the prior art, in particular without major catalyst losses by abrasion or discharge be feasible and can be done with fewer and shorter interruptions of operation. Furthermore, the method should be able to be carried out with relatively simple and inexpensive systems. The plants should accordingly be associated with low investment costs. Here, the facilities should be easy to maintain, cause low maintenance costs and be safe to operate.
- the reactor has at least two zones. In zone 1, the reaction mixture is conveyed downwards. In zone 2, the reaction mixture is again conveyed upwards. The zones 1 and 2 are separated by a partition wall. During reactor operation, generally less catalyst mass per unit volume remains in zone 1 than in zone 2. Thus, the ratio between the average catalyst concentrations in zone 2 and in zone 2 is
- Zone 1 is greater than 2, preferably greater than 5, in particular greater than 10 and particularly preferably greater than 20. In very particularly preferred embodiments of the present invention, the ratio between the average catalyst concentrations in zone 2 and in zone 1 is even greater than 100.
- Zone 1 optimally has a turbulent flow and therefore a very fast one
- Zone 2 at least in the upper part has a laminar flow, which is conducive to optimal catalyst deposition.
- a feature of a preferred embodiment of the present invention is the existence of a concentration gradient along the reactor height in zone 2: the largest portion of the complete catalyst mass is in the lower part of zone 2, while only a fraction of it is in the upper part of zone 2.
- This ratio is particularly preferably less than 0.2, more preferably less than 0.1, and most preferably less than 0.05. While thus forms a catalyst concentration profile according to the invention in the zone 2, which remains
- Catalyst concentration in the zone 1 more or less constant at the level of the minimum catalyst concentration in the upper part of the zone 2.
- Catalyst concentration distribution can in turn be generated by an optimized flow course within the reactor. For this purpose, the statements made below can be applied.
- the ratio between the average vertical flow velocity in zone 1 and the average vertical flow velocity in zone 2 is between 2 and 100, more preferably between 5 and 50 and especially preferably between 10 and 40.
- the internal circulation between the zones 1 and 2 in the reactor - regardless of the other settings of the method - ensured by means of an inner tube (7).
- Reaction mixture in the inner tube (zone 1) generated in the flow direction down, while in the outer zone 2, a counter-flow - is generated from bottom to top. This zone 2 is then the area between the inner tube and the reactor walls.
- Zone 1 is preferably a cylindrical inner tube, wherein the diameter of this inner tube can be varied along the reactor height.
- the lower part of the tube has a smaller diameter than the upper part of this tube.
- zone 1 in the upper part facilitates a smooth transition between the turbulent zone 1 and the laminar zone 2 and thus less catalyst in zone 1 is entrained.
- the preferred ratio between the diameter of the tube in the upper and lower part of the zone 1 is between 1 and 5, preferably between 2 and 4.
- the reactor preferably has a typical cylindrical shape for pressure reactors, rounded in the lower and upper part. The optimal ratio between the reactor height and the
- Reactor diameter is preferably between 1 and 3, more preferably between 1, 1 and 2.5, most preferably between 1, 3 and 2.3.
- the diameter of the reactor can be varied along the reactor height. For example, e.g.
- the lower part of the reactor has a smaller diameter than the upper part of this reactor.
- another adjustable feature of the invention is the ratio of the reactor diameter in the upper part to that in the lower part, which is preferably between 1 and 2, preferably between 1.1 and 1.5.
- the ratio between the maximum and the minimum reactor diameter is between 1 and 2, particularly preferably between 1.1 and 1.5.
- the phrase "in the upper part” should be determined such that a measurement is measured 10% of the total height below the top of each area corresponding to 10% above the lower end of the total height is selected as a measuring point. It is important for more accurate determination that the distance to the upper or lower end is identical, and that this distance to the measurement a maximum of a distance equal to 20% of the total height of the device to be measured (for example, zone 1 or total reactor) from the respective upper and lower End of the device is removed.
- Sedimentation of the catalyst can be effected.
- significantly less non-deposited catalyst from zone 2 can get into zone 1 and thus a much lower
- Reaction mixture in the zone 1 preferably conveyed downwards by means of at least one pump or at least one stirrer. All stirrers that promote an axial flow down would be particularly suitable for this purpose. At least one particularly preferred at least two propeller stirrers are preferably used. In the case of a stirrer, this is preferably approximately in the middle of the
- Inner tube is placed, while two stirrers are preferably installed in the middle and at the bottom of the inner tube.
- At least one liquid feed stream is preferably introduced into the upper part of zone 1.
- the reactor should preferably be used for a continuous process, preferably the heterogeneous catalyst should be filtered off from the reaction mixture continuously.
- filters are preferably used in the reactor, particularly preferably at the periphery in the upper part of the zone 2 of the reactor.
- at least one continuously operable and backwashable filter is preferably installed in the upper part of zone 2.
- the reaction mixture is continuously discharged from the reactor and filtered through at least one external filter.
- the catalyst is optionally further treated after filtration and passed partially or completely back into the reactor. This further treatment may, for example, be a washing,
- Reactivate or a separation according to particle sizes act.
- an additional deposition system can be installed prior to such filters. This can be a special zone with laminar flow, where sedimentation of a large part of the catalyst used takes place. Such sedimentation occurs before it comes to the actual filtration.
- a possible variant of such a sedimentation system is e.g. a complex of tilted elements such as e.g. Tubes or sloped metal sheets (e.g., a skewer).
- tilted elements such as e.g. Tubes or sloped metal sheets (e.g., a skewer).
- the sedimentation system and filter in the upper part of the reactor are in such a position of zone 2 that the flow velocity is slowest there. This in turn means that the cross-section of zone 2 has a maximum area at this point.
- the preferred filter porosity is between 5 and 100 micrometers, more preferably between 10 and 50 micrometers.
- reaction mixture filtered once via reactor filter (5) is preferably filtered at least once more via finer filters with a porosity of 1 to 10 ⁇ outside the reactor, so that the particles of at most 5 ⁇ to at least 90% of retained by the filter.
- the reaction mixture after the sedimentation system (4) passes through a plurality of filters (5) uniformly distributed around the reactor and reaches the further product processing steps.
- the filter and sedimentation system is preferably backwashed regularly, so that a maximum amount of heterogeneous catalyst remains catalytically active in the reactor and no blockage of the sedimentation system and the filter takes place.
- one or more flow breakers (10), so-called swirl breakers, may preferably be located in the upper part of zone 1.
- the zone 2 with at least 2, more preferably with at least 4, most preferably with at least 8 flow breaker and / or
- the gas required for the reaction via the gas distributor (9), so-called sparger, metered in the finely dispersed state in the lower part of the reactor.
- the gas used is metered in the direction of the reactor bottom, so that the least possible blockage with the catalyst particles can occur.
- hydrogen or hydrogen-containing gas is suitably used.
- oxygen is used in the form of air or another O 2 -containing mixture.
- synthesis gas can serve as a gas.
- Other unnamed gases can be used depending on the desired reaction.
- a suitable liquid phase application for the described reactor is e.g. the hydrogenation of anthraquinone used for hydrogen peroxide production.
- it can be a fat hardening, ie hydrogenation of unsaturated fatty acids operated.
- Numerous other hydrogenations e.g. multi-bond materials such as aromatics, alkenes or alkynes, nitro compounds, carbonyl compounds, etc. can also be made with the reactor type.
- the process according to the invention is particularly preferably applicable to a heterogeneously catalyzed oxidation reaction with an oxygen-containing gas.
- the process according to the invention is particularly preferably applicable to a heterogeneously catalyzed oxidation reaction with an oxygen-containing gas.
- Oxygen concentration (C partial pressure) in zone 2 a gradient with a maximum O2 concentration in the lower part of zone 2 and a minimum C concentration in the upper part of this zone.
- the ratio between the oxygen concentration in the gas phase of zone 2 to 20% of the fill level of the reactor measured from below and the oxygen concentration in the gas phase of zone 2 to 90% of the fill level measured from below is particularly preferably greater than 2 greater than 4.
- Some examples of the appropriate oxidation processes in the liquid phase are e.g. special oxidations of alkenes, alkylaromatics, oxidative esterification of aldehydes to
- Carboxylic acid esters such as the reaction of (meth) acrolein to alkyl (meth) arylate, and further selective oxidation reaction in the field of specialty chemistry.
- the heterogeneously catalyzed reaction is a continuous oxidative esterification of methacrolein with oxygen and methanol
- the heterogeneous catalysts used are preferably noble metal-containing, in particular Pt, Pd, Ru, Rh, Ru, Au and / or Ag-containing, supported catalysts.
- Pt, Pd, Ru, Rh, Ru, Au preferably, gold
- Ag-containing, supported catalysts preferably, mineral oxides, oxide mixtures, activated carbon, polymer materials or other substances.
- a catalyst preferably used for such an oxidation reaction has an average diameter of between 10 and 200 ⁇ m.
- the catalyst used may be e.g. for a washing and / or regeneration process, for continuous monitoring / analysis or renewal of the reactor continuously or
- the catalyst removal or feed interface is preferably in the lower part of the reactor where the catalyst concentration is highest.
- An alternative preferred variant implies a catalyst removal point in the upper part of the reactor. In this case, preference is given to a site at which, in particular, the smallest catalyst particles are located.
- various adjuvants such as e.g. Acids, bases, polymerization inhibitors, anti-foaming agents, etc. are fed to the process.
- All highly reactive (e.g., readily polymerizable) starting materials and / or adjuvants e.g. a strong base, such as NaOH or KOH, or a strong acid, such as H2SO4 or HCl, are preferably metered into the upper part of zone 1. This ensures that these substances are mixed as quickly as possible with the reaction mixture before they can come into contact with the catalyst and the other reactants. This avoids local overheating and improves the selectivity and overall efficiency of the target reaction.
- a strong base such as NaOH or KOH
- a strong acid such as H2SO4 or HCl
- FIG. 1 LIST OF REFERENCES FIG. 1
- FIG. 1 is the specific embodiment of a reactor which can be used in the method according to the invention. This represents a particularly suitable for oxidation reactions embodiment of the invention.
- the drawing is not intended to limit the scope of the present application in any way. In this case, this drawing is simplified so that tapers of the reactor or the zone 1, for example, are not shown.
- Motor a Feed 1 (educt 1)
- reaction mixture level b (optional) Feed 2 (starting material 2)
- reaction zone zone 2, lower part
- zone 2 air was metered in via several gas distributors.
- the product mixture was separated from most of the heterogeneous catalyst via a continuously backflushable settling system (oblique clarifier) located at the periphery of the top of Zone 2 and filtered through a filtration system and analyzed by gas chromatography (GC).
- GC gas chromatography
- Zone 2 The ratio C90% / C20% in Zone 2 was less than 0, 1.
- the average concentration in Zone 1 ⁇ C1> was calculated as the mean of the three samples from the inner tube:
- ⁇ C1> (C1 (20%) + C1 (50%) + C1 (90%)) / 3, where C1 was (20%) ⁇ C1 (50%) ⁇ C1 (90%); the average concentration in zone 2 ⁇ C2> was calculated as follows:
- ⁇ C1> (total catalyst mass - ⁇ C1> * V1) / V2 ⁇ C2> / ⁇ C1> was greater than 10
- zone 2 air introduced via air distributor could be observed during operation almost exclusively in zone 2, while zone 1 at least remained free from the gas undissolved in the reaction mixture.
- Oxygen concentration in the gas phase of zone 2 to 20% of the bottom of the measured filling height of the reactor was C (O2) 20% -21 vol% 02
- oxygen concentration in the gas phase of zone 2 to 90% of the measured from below filling level was C (O 2 ) 90% ⁇ 5 vol% 0 2
- C (O 2 ) 20% / C (O 2 ) 90% 4.2 This ensured a continuous trouble-free operation of the system for several months.
- Example 2 Similar to Example 1 but without internal filter in the reactor after the settling system.
- the reaction mixture was alternately filtered through one of two 10 micron porosity external filters installed in parallel with one filter in constant use and the other backwashed simultaneously.
- the catalyst remaining on the filter was returned to the reactor. This ensured a continuous trouble-free operation of the system for several months.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16166606.0A EP3235560A1 (de) | 2016-04-22 | 2016-04-22 | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
PCT/EP2017/058903 WO2017182381A1 (de) | 2016-04-22 | 2017-04-13 | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3445483A1 true EP3445483A1 (de) | 2019-02-27 |
Family
ID=55862558
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16166606.0A Withdrawn EP3235560A1 (de) | 2016-04-22 | 2016-04-22 | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
EP17716925.7A Withdrawn EP3445483A1 (de) | 2016-04-22 | 2017-04-13 | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16166606.0A Withdrawn EP3235560A1 (de) | 2016-04-22 | 2016-04-22 | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
Country Status (11)
Country | Link |
---|---|
US (1) | US10596539B2 (de) |
EP (2) | EP3235560A1 (de) |
JP (1) | JP6873155B2 (de) |
KR (1) | KR102352909B1 (de) |
CN (1) | CN109070036B (de) |
BR (1) | BR112018071599A2 (de) |
RU (1) | RU2731571C2 (de) |
SA (1) | SA518400269B1 (de) |
SG (1) | SG11201809192YA (de) |
TW (1) | TW201806666A (de) |
WO (1) | WO2017182381A1 (de) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3658529A1 (de) * | 2017-07-28 | 2020-06-03 | Rohm and Haas Company | Verfahren zur herstellung von methylmethacrylat durch oxidative veresterung unter verwendung eines heterogenen katalysators |
US10829432B2 (en) * | 2017-07-28 | 2020-11-10 | Dow Global Technologies Llc | Method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
EP3658534A1 (de) * | 2017-07-28 | 2020-06-03 | Rohm and Haas Company | Verfahren zur herstellung von methylmethacrylat durch oxidative veresterung unter verwendung eines heterogenen katalysators |
KR102639247B1 (ko) * | 2017-07-28 | 2024-02-21 | 다우 글로벌 테크놀로지스 엘엘씨 | 불균일 촉매를 사용하여 산화적 에스터화에 의해 메틸 메타크릴레이트를 제조하는 방법 |
CN111051274A (zh) * | 2017-07-28 | 2020-04-21 | 陶氏环球技术有限责任公司 | 通过使用非均相催化剂进行氧化酯化来生产甲基丙烯酸甲酯的方法 |
KR102563776B1 (ko) * | 2017-07-28 | 2023-08-04 | 다우 글로벌 테크놀로지스 엘엘씨 | 불균일 촉매를 사용하여 산화적 에스터화에 의해 메틸 메타크릴레이트를 제조하는 방법 |
US10865179B2 (en) * | 2017-09-19 | 2020-12-15 | Dow Global Technologies, Llc | Method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
CN108671877B (zh) * | 2018-07-16 | 2024-02-20 | 山东绿色自由基科技研究中心 | 一种多相流非均相反应器 |
EP4347548A1 (de) | 2021-05-28 | 2024-04-10 | Röhm GmbH | Reaktor und verfahren zur herstellung von alkyl(meth)acrylaten |
KR20240014487A (ko) | 2021-05-28 | 2024-02-01 | 룀 게엠베하 | 알킬 메타크릴레이트를 제조하기 위한 반응기 및 방법 |
WO2023059674A1 (en) * | 2021-10-08 | 2023-04-13 | Dow Global Technologies Llc | Process for low byproduct formation from an oxidative esterification reactor with base addition |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2101111T3 (es) | 1991-07-29 | 1997-07-01 | Exxon Chemical Patents Inc | Reactor de polimerizacion. |
US5288673A (en) | 1992-12-18 | 1994-02-22 | Exxon Research And Engineering Company | Temperature control in draft tubes for catalyst rejuvenation |
US5569434A (en) * | 1994-10-10 | 1996-10-29 | Amoco Corporation | Hydrocarbon processing apparatus and method |
US5723041A (en) * | 1994-10-10 | 1998-03-03 | Amoco Corporation | Process and apparatus for promoting annularly uniform flow |
US5856533A (en) * | 1995-12-28 | 1999-01-05 | Praxair Technology, Inc. | High efficiency heat and mass transfer for vapor phase heterogeneous reactions |
JP3874442B2 (ja) | 1996-03-18 | 2007-01-31 | 旭化成エンジニアリング株式会社 | 液成分の連続分離装置 |
JP3874470B2 (ja) | 1996-09-24 | 2007-01-31 | 旭化成エンジニアリング株式会社 | メタクリル酸メチル製造装置 |
US5962537A (en) | 1997-05-06 | 1999-10-05 | Exxon Research And Engineering Co | Multizone downcomer for slurry hydrocarbon syntheses process |
SG71815A1 (en) | 1997-07-08 | 2000-04-18 | Asahi Chemical Ind | Method of producing methyl methacrylate |
SG123723A1 (en) * | 2004-12-22 | 2006-07-26 | Sumitomo Chemical Co | Process for producing cyclohexanone oxime |
US8236170B2 (en) * | 2005-12-16 | 2012-08-07 | Chevron U.S.A. Inc. | Reactor for use in upgrading heavy oil |
CN101314120B (zh) | 2007-05-31 | 2010-05-26 | 中国石油化工股份有限公司 | 一种浆态床反应器及其应用 |
RU2437715C1 (ru) * | 2007-10-26 | 2011-12-27 | Асахи Касеи Кемикалз Корпорейшн | Материал с композитными частицами на подложке, способ его получения и способ получения соединений с использованием материала с композитными частицами на подложке в качестве катализатора для химического синтеза |
US8119014B2 (en) * | 2008-12-23 | 2012-02-21 | Exxonmobil Research And Engineering Company | Systems and methods to remove liquid product and fines from a slurry reactor |
CN102773048B (zh) | 2011-05-09 | 2017-06-06 | 波利玛利欧洲股份公司 | 生产环己酮肟的氨肟化反应器 |
JP6501754B2 (ja) | 2013-04-19 | 2019-04-17 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | メチルメタクリレートの製造方法 |
CN104418309B (zh) | 2013-09-05 | 2016-08-17 | 中国石油化工股份有限公司 | 一种过氧化氢的制备方法 |
EP2886528A1 (de) | 2013-12-20 | 2015-06-24 | Evonik Industries AG | Verfahren zur Herstellung von ungesättigten Estern ausgehend von Aldehyden durch Direkte Oxidative Veresterung |
EP2886529A1 (de) | 2013-12-20 | 2015-06-24 | Evonik Industries AG | Verfahren zur Herstellung von Methylmethacrylat |
CN105126710B (zh) * | 2015-08-28 | 2017-05-10 | 湖南百利工程科技股份有限公司 | 一种浆态床反应器及其在生产过氧化氢中的应用 |
-
2016
- 2016-04-22 EP EP16166606.0A patent/EP3235560A1/de not_active Withdrawn
-
2017
- 2017-04-13 WO PCT/EP2017/058903 patent/WO2017182381A1/de active Application Filing
- 2017-04-13 CN CN201780024248.3A patent/CN109070036B/zh active Active
- 2017-04-13 SG SG11201809192YA patent/SG11201809192YA/en unknown
- 2017-04-13 KR KR1020187030410A patent/KR102352909B1/ko active IP Right Grant
- 2017-04-13 BR BR112018071599-9A patent/BR112018071599A2/pt not_active Application Discontinuation
- 2017-04-13 JP JP2018555248A patent/JP6873155B2/ja active Active
- 2017-04-13 RU RU2018140981A patent/RU2731571C2/ru active
- 2017-04-13 US US16/095,065 patent/US10596539B2/en not_active Expired - Fee Related
- 2017-04-13 EP EP17716925.7A patent/EP3445483A1/de not_active Withdrawn
- 2017-04-19 TW TW106113136A patent/TW201806666A/zh unknown
-
2018
- 2018-10-18 SA SA518400269A patent/SA518400269B1/ar unknown
Also Published As
Publication number | Publication date |
---|---|
KR102352909B1 (ko) | 2022-01-18 |
JP2019514880A (ja) | 2019-06-06 |
CN109070036A (zh) | 2018-12-21 |
KR20180136958A (ko) | 2018-12-26 |
CN109070036B (zh) | 2022-06-03 |
EP3235560A1 (de) | 2017-10-25 |
BR112018071599A2 (pt) | 2019-02-12 |
RU2018140981A (ru) | 2020-05-22 |
WO2017182381A1 (de) | 2017-10-26 |
US10596539B2 (en) | 2020-03-24 |
TW201806666A (zh) | 2018-03-01 |
SG11201809192YA (en) | 2018-11-29 |
JP6873155B2 (ja) | 2021-05-19 |
RU2018140981A3 (de) | 2020-05-22 |
SA518400269B1 (ar) | 2021-12-06 |
US20190099731A1 (en) | 2019-04-04 |
RU2731571C2 (ru) | 2020-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3445483A1 (de) | Verfahren zur durchführung einer heterogen-katalysierten reaktion | |
EP3083549B1 (de) | Verfahren zur herstellung von ungesättigten estern ausgehend von aldehyden durch direkte oxidative veresterung | |
EP1637220B1 (de) | Rührvorrichtung und Verfahren zur Durchführung einer Gas-Flüssig-Reaktion | |
EP2162206B1 (de) | Verfahren zum einbringen einer wenigstens einer produktionscharge von ringförmigen schalenkatalysatoren k entnommenen teilmenge in ein reaktionsrohr eines rohrbündelreaktors | |
EP0798039B2 (de) | Verfahren zur Durchführung von Stoffumwandlungen mit in Flüssigkeiten suspendierten Katalysatoren | |
DE60028408T2 (de) | Verfahren und vorrichtung zur reinigung von wässrigen abfällen durch katalytische oxidation | |
EP2280922A1 (de) | Verfahren zur herstellung und aufreinigung wässriger phasen | |
EP3621943B1 (de) | Verfahren für oxidative veresterung von aldehyden zu carbonsäureester | |
DE102007004558A1 (de) | Verfahren zur Herstellung eines tertiären Amins | |
EP0947493B1 (de) | Verfahren zur selektiven Flüssigphasenhydrierung von alpha,beta-ungesättigten Carbonylverbindungen | |
JP5640493B2 (ja) | 分離ユニット、分離装置、分離方法およびα,β−不飽和カルボン酸の製造方法 | |
EP2943272B1 (de) | Vorrichtung und verfahren zur kontinuierlichen umsetzung von flüssigkeiten mit gasen | |
EP3423183B1 (de) | Mehrphasen-schlaufenreaktor und verfahren zum betrieb | |
EP2943273B1 (de) | Vorrichtung und verfahren zur kontinuierlichen umsetzung von flüssigkeiten mit gasen | |
EP0000902B1 (de) | Verfahren zur Herstellung von Hydroxylammoniumsalze | |
EP2050732A1 (de) | Verfahren zum ersatz eines dispersionsmediums | |
EP0515799B1 (de) | Reaktor für phasenheterogene Reaktionen | |
WO2001032557A1 (de) | Verfahren zur herstellung von wasserstoffperoxid | |
DE2007371A1 (de) | Verfahren und Vorrichtung zur Kontaktbehandlung von Feststoffen, Flüssigkeiten und Gas | |
EP2455360A1 (de) | Apparat zum Ersetzen eines Dispersionsmediums | |
WO2005046857A1 (de) | Vorrichtung zur durchführung von flüssig-reaktionen mit feinkörnigen feststoffkatalysatoren und verfahren für dessen anwendung | |
DE1542089C3 (de) | ||
AT275481B (de) | Verfahren zur Durchführung von katalytischen Hydrierungsreaktionen in Gegenwart von Suspensionskatalysatoren |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20181016 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ROEHM GMBH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: ROEHM GMBH |
|
17Q | First examination report despatched |
Effective date: 20200710 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20230725 |