EP3322778A1 - Device and method for producing synthetic gas - Google Patents
Device and method for producing synthetic gasInfo
- Publication number
- EP3322778A1 EP3322778A1 EP16757688.3A EP16757688A EP3322778A1 EP 3322778 A1 EP3322778 A1 EP 3322778A1 EP 16757688 A EP16757688 A EP 16757688A EP 3322778 A1 EP3322778 A1 EP 3322778A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- natural gas
- syngas
- synthetic natural
- methanation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007789 gas Substances 0.000 claims abstract description 52
- 238000000926 separation method Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000002309 gasification Methods 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 81
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 49
- 230000015572 biosynthetic process Effects 0.000 claims description 39
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 238000011144 upstream manufacturing Methods 0.000 claims description 22
- 238000002347 injection Methods 0.000 claims description 21
- 239000007924 injection Substances 0.000 claims description 21
- 239000003345 natural gas Substances 0.000 claims description 19
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 4
- 231100000167 toxic agent Toxicity 0.000 claims description 3
- 239000000047 product Substances 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000011269 tar Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- -1 for example Chemical class 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000009491 slugging Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LMMJFBMMJUMSJS-UHFFFAOYSA-N CH5126766 Chemical compound CNS(=O)(=O)NC1=NC=CC(CC=2C(OC3=CC(OC=4N=CC=CN=4)=CC=C3C=2C)=O)=C1F LMMJFBMMJUMSJS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/106—Removal of contaminants of water
Definitions
- the present invention relates to a device and a method for producing synthesis gas. It applies, in particular, to the production of synthetic natural gas by gasification of hydrocarbon compounds.
- biomethane belonging to the "SNG” (Synthesis Natural Gas, translated by Natural Gas Synthesis) can be achieved by thermochemical conversion of any hydrocarbon compound. This conversion is carried out by a process consisting of four main stages that are:
- syngas synthesis gas essentially composed of H 2, CO, CO 2, CH 4 , H 2 O and Tars (C 6 + tar)
- PCS PCS
- HHV High English
- the gasification of the hydrocarbon compound is carried out in a reactor in which the biomass undergoes different reaction stages.
- the first step corresponds to a thermal degradation of the hydrocarbon compound which successively undergoes drying and devolatilization of the organic material to produce:
- a synthesis gas such as H 2 , CO, CO 2 , H 2 O and CH 4 and
- condensable compounds contained in the syngas such as tar or tars
- the carbonaceous residue can then be oxidized by a gasifying agent, such as water vapor, air, or oxygen, to produce H2, CO.
- a gasifying agent such as water vapor, air, or oxygen
- this gasification agent may also react with tars or major gases.
- WGS Water Gas Shift, translated by reaction gas to water
- the reactor pressure has little effect on this reaction.
- the equilibrium is strongly related to the temperature of the reactor and to the "initial" contents of the reagents.
- the H2 / CO ratio is generally less than 2 at the end of the gasification step. This ratio is an important factor for the production of biomethane during the subsequent purification and methanation steps that allow the production of the CHU and on which the SNG production process is based.
- the WGS reaction can be carried out in a specific reactor placed upstream of the methanation. However, in the case of certain fluidized bed processes, the two methanation and WGS reactions can be carried out in parallel in the same reactor; the steam required for the WGS reaction is injected into the reactor together with the reaction mixture.
- the methanation reaction is an exothermic reaction with a decrease in the number of moles; according to the Le Chatelier principle, the reaction is favored by the increase of the pressure and disadvantaged by the increase of the temperature.
- the production of methane from CO and H2 is optimal for a composition gas close to the stoichiometric composition, that is to say whose H2 / CO ratio is close to 3.
- the syngas produced by gasification, in particular of biomass is characterized by a lower H2 / CO ratio, of the order of 1 to 2. Also, to maximize the methane production, this ratio must be adjusted by producing hydrogen by reaction between carbon monoxide and water vapor by the reaction of WGS.
- the nickel component of the catalyst or present in the reactor wall material is capable of reacting with carbon monoxide to form nickel tetra-carbonyl (Ni (CO) 4) , very highly toxic compound. This is why it is essential that all parts of the reactor in the presence of CO and metal compound are always at a temperature above 150 ° C and preferably above 230 ° C to avoid it completely.
- the heat generated during the CO conversion is about 2.7 kWh when producing 1 Nm 3 of methane. Controlling the temperature in the reactor, and thus eliminating the heat produced by the reaction, is one of the key points in minimizing the deactivation of the catalyst, by sintering, and maximizing the conversion rates to methane.
- the implementation of a fluidized reactor is a simple solution to limit the reaction temperature.
- the fluidization of the catalyst by the reaction mixture allows an almost perfect homogenization of the temperatures in all points of the catalytic layer and the reactor can be likened to an isothermal reactor.
- the heat produced by the reaction is removed by means of exchangers immersed in the fluidized bed.
- the heat exchange coefficients between the fluidized layer and a wall immersed in the bed are very important (of the order of 400 to 600 W / Km 2 , comparable to those between a liquid and a wall) and make it possible to minimize the dimensions. of the exchanger and therefore the overall size of the reactor.
- the kinetics of the methanation reaction is very fast, and therefore the amount of catalyst required simply because of the chemical reaction is low. Also the size of the reactor and the amount of catalyst used result from the bulk of the exchanger implanted within the fluidized bed.
- slugging corresponds to the displacement of solid per package with, between two packets, a gas pocket which encumbrates the entire section of a reactor, which has the effect of obtaining alternation between solid and gaseous packages in place of a mixture of gas and gas. solid as expected and - modification of the physical characteristics of the catalyst (particle size, density of the support) to maintain an equivalent fluidization for a lower volume flow rate.
- the fluidized bed inherently allows for greater flexibility in terms of flow rate and thus reactor power around the sizing conditions.
- the final step of specification is to separate the constituents of the gas from the methanation to obtain a biomethane meeting the injection specifications on the natural gas network.
- this separation generates by-products that are H2O, CO2 and H2. It is most often performed in separate equipment with sometimes very different operating conditions.
- the water is first separated from the biomethane by cooling and condensation passing below the dew point temperature of the water under the conditions considered.
- the CO2 is extracted from the gas to reach the specifications of the network.
- the technologies allowing this separation are relatively numerous and known.
- the main technological families are the absorption, physical or chemical, adsorption modulated in pressure, membrane permeation or cryogenics.
- the composition of the crude SNG at the outlet of the reactor is intimately related to the operating conditions of the reactor, in terms of pressure, temperature, the adiabatic or isothermal mode of operation of the reactor, and these conditions govern the chemical equilibrium of the reactions above. These reactions generally form water and a separation of this species is therefore required. Concerning the other species (CO, CO2 and H2), their respective contents can be modified by playing on the one hand on the mode of operation of the reactor (adiabatic or isothermal) and on the other hand on the temperature or the pressure. High pressure and low temperature will thus allow to considerably reduce the contents of these compounds. When the operation is carried out in "adiabatic" reactor, a succession of steps is also necessary to achieve a conversion quality equivalent to the isothermal reactor. In any case, the composition of the product gas is generally incompatible with respect to the injection specifications, therefore improvement steps are necessary to remove residual CO 2 and / or H 2. Thus, the procedure constitutes a lock for the simplification of the process chain.
- This recirculation of methanation products aims, according to this document, to adjust the temperature of the reagents entering the adiabatic methanation reactor in order to moderate the exothermicity of the adiabatic reaction occurring in the reactor.
- the temperature reached at the inlet of the methanation reactor is of the order of 310 to 330 ° C. and the temperature at the outlet of this reactor is of the order of 620 ° C., which induces a limited inefficient conversion.
- undesirable compounds such as, for example, H2, CO, CO2 in excess in the stream leaving the reactor.
- This presence of undesirable compounds, especially dihydrogen requires a step of separation of the hydrogen downstream of the reactor to meet, for example, injection specifications on the natural gas distribution or transport network.
- PCS Higher Heating Value
- This recirculation of methanation products aims, according to this document, to adjust the temperature of the reagents entering the adiabatic methanation reactor in order to moderate the exothermicity of the adiabatic reaction occurring in the reactor.
- Adiabatic reactors if they do not involve internal cooling in the methanation reactor, have several disadvantages:
- the design of the adiabatic reactors is simpler because they consist essentially of a chamber to withstand generally high pressures (> 30 bar) to achieve a satisfactory conversion.
- the operating pressure does not need to be as important ( ⁇ 20 bar) but requires the disposal of immersed surfaces within the catalytic layer, which generates a complexity of design and a additional cost related to the cooling system.
- the present invention aims to remedy all or part of these disadvantages.
- the present invention provides a device for producing synthesis gas, which comprises:
- an isothermal methanation reactor comprising:
- the device which is the subject of the present invention allows simplified design of the reactor as well as simplification of the setting to specifications no longer requiring separation of the hydrogen before conditioning for injection into the gas network.
- an isothermal reactor allows the realization of a single step of methanation to obtain an efficient conversion to synthetic natural gas and obtain a quality gas close to the injection specifications on the distribution network or transport of natural gas.
- the device which is the subject of the present invention comprises means for separating carbon dioxide from the dehydrated synthetic natural gas, this separation means being positioned downstream of the bypass.
- the device which is the subject of the present invention comprises means for separating carbon dioxide from the dehydrated synthetic natural gas, this separation means being positioned upstream of the bypass.
- the device which is the subject of the present invention comprises: a sensor of a temperature inside or at the outlet of the reactor and
- the device which is the subject of the present invention comprises, upstream of the inlet of the reactor, a means for preheating the mixture at a temperature greater than 150 ° C.
- the preheating means heats the mixture to a temperature above 230 ° C to prevent the production of toxic compounds and below the operating temperature of the reactor to allow cooling of the reactor.
- the device that is the subject of the present invention comprises a pipe for injecting water vapor into the syngas supply pipe upstream of the site where the mixture between the syngas and the methanation products issued from the derivation.
- the device which is the subject of the present invention comprises a deflection conduit, a part of the hot products of methanation reactions, comprising:
- the device that is the subject of the present invention comprises:
- a recirculator a recirculator, products entered in the bypass line, the recirculator being controlled as a function of the measured flow rate.
- the water separation means configured to cool synthetic natural gases to a temperature of -5 ° C to + 60 ° C.
- the water separation means is configured to cool the synthesis natural gas to a temperature below the dew point temperature of the water at the operating pressure of the reactor of interest.
- the reactor is configured to perform a Dussan reaction called "gas to water”.
- the isothermal reactor is a fluidized bed reactor.
- the device that is the subject of the present invention comprises at least one heat exchange surface positioned in the fluidized bed.
- the present invention relates to a process for producing synthesis gas, which comprises:
- a methanation reaction step comprising:
- a step of separating water comprising:
- the method which is the subject of the present invention comprises:
- a deflection step a portion of the hot products of methanation reactions upstream of the methanation step.
- FIG. 1 represents, schematically, a first particular embodiment of the device that is the subject of the present invention
- FIG. 2 represents, schematically, a second particular embodiment of the device that is the subject of the present invention
- FIG. 3 represents, schematically and in the form of a logic diagram, a particular sequence of steps of the method which is the subject of the present invention
- FIG. 4 represents, in the form of a curve, the synthesis gas Wobbe index obtained by the device and method that are the subject of the present invention
- FIG. 5 represents, in the form of a curve, the PCS of synthesis gas obtained by the device and method that are the subject of the present invention
- FIG. 6 represents, in the form of a curve, the relative decrease of the molar flow of dihydrogen in the synthesis gas as a function of the recirculation rate of the synthesis gas
- FIG. 7 represents, in the form of a curve, the exothermicity of the reaction for obtaining synthesis gas during the implementation of the device and the method which are the subject of the present invention and
- Figure 8 shows schematically an example of a system implemented in the state of the art.
- each feature of an embodiment being able to be combined with any other feature of any other embodiment in an advantageous manner.
- each parameter of an exemplary embodiment can be implemented independently of other parameters of said exemplary embodiment.
- FIG. 8 shows a schematic view of an exemplary system 80 implemented in the state of the art.
- methanation reagents enter a methanation reactor 805 which may be part of a series (not shown) of such reactors.
- the water is separated from the methanation products via a separation means 825 of this water, such as a heat exchanger for example.
- the dehydrated synthetic natural gas is then treated with carbon dioxide separation means 845.
- the synthetic natural gas is treated by a means 855 for separating dihydrogen so that this synthetic natural gas is to the injection specifications on a distribution network.
- the steps of separating water, carbon dioxide and dihydrogen can be carried out in any order.
- FIG. 1 which is not to scale, shows a schematic view of a first embodiment of the device 10 which is the subject of the present invention.
- This device 10 for producing synthesis gas comprises:
- an isothermal methanation reactor 105 comprising:
- means 125 for separating water comprising:
- a bypass 140 of a portion of the dehydrated synthetic natural gas from the outlet of the water separation means 125 to the syngas feed line 1 for a synthetic syngas and syngas mixture is supplied to reactor 105.
- the reactor 105 is, preferably, an isothermal fluidized bed methanation reactor operating at a predetermined temperature.
- the fluidization of the catalyst by the reaction mixture allows an almost perfect homogenization of the temperatures in all points of the catalytic layer and the reactor can be likened to an isothermal reactor.
- this reactor 105 may be a boiling water reactor, known to those skilled in the art under the abbreviation "BWR" (Boiling Water Reactor, translated by boiling water reactor).
- this reactor 105 may be a wall-cooled bed reactor or an exchanger reactor.
- the reactor 105 has at least one heat exchange surface 106 positioned in the fluidized bed of the isothermal reactor 105.
- This surface 106 is, for example, a tube configured to form a circulation loop of a fluid from the outside of the reactor 105 to the interior of this reactor 105, the fluid being cooled outside the reactor 105.
- This fluid is, for example, saturated or superheated steam.
- This reactor 105 is configured to perform the methanation of carbon monoxide and / or carbon dioxide.
- This reactor 105 has the input 10 for syngas which is, for example, an orifice of the reactor 105 provided with a connector (not shown) compatible with the syngas supply line.
- the reactor 105 is configured to perform a Dussan reaction called "gas to water".
- water vapor is injected into the syngas supplied to the reactor 105.
- the syngas feed line 1 is connected to a gasification unit for hydrocarbon materials (not shown), such as biomass, coal or waste.
- the syngas has elements of hb, CO, CO2, H2O, CHU, C2, C3 +, and so on.
- This supply line 1 15 is sealed.
- the supply line 115 receives H2 from, for example, a water electrolysis device.
- the supply line 115 receives H2 from a plurality of separate sources.
- the synthetic natural gases leave the reactor 105 through the outlet 120 of the reactor.
- This output 120 is, for example, an orifice connected to a connector (not shown) for fixing a sealed pipe for transporting synthetic natural gas.
- the water separating means 125 is, for example, a heat exchanger for cooling the natural synthesis gases to a temperature below the dew point temperature. some water. This temperature is preferably between -5 ° C and + 60 ° C. Preferably, this temperature is between -5 ° C and 40 ° C.
- the water thus separated is collected by an outlet 127 for water and can be used by an external device or heated to be transformed into water vapor which, as indicated below, to be injected into the supply line 1 15 of syngas.
- the water separating means 125 comprises the inlet 130 for synthetic natural gas.
- This inlet 130 is, for example, an orifice associated with a connector (not shown) to be connected to the sealed pipe for transporting the synthetic natural gas from the reactor 105.
- This sealed transport pipe is connected to the outlet 120 for gas natural synthesis of the methanation reactor 105.
- the water separating means 125 comprises the outlet 135 for dehydrated synthetic natural gas.
- This output 135 is, for example, a port associated with a connector (not shown) to be connected to a sealed conduit (not shown) for transporting dehydrated synthetic natural gas.
- the bypass 140 is, for example, a sealed pipe connected to the dehydrated synthetic natural gas transport pipe for capturing part of the flow passing through this transport pipe.
- This bypass 140 injects the dehydrated synthetic natural gas into the syngas feed line.
- syngas and dehydrated synthetic natural gas cooled by the water separation process, form a mixture which, in reactor 105, reduces the exothermicity of the methanation reactor while improving the characteristics of the gas. natural synthesis from the reactor 105 to meet the usual specifications of use.
- the device 10 comprises:
- a recirculator 155 products entered in the bypass, this recirculator being controlled as a function of the sensed temperature.
- the sensor 150 is positioned inside or at the outlet of the reactor 105. This sensor 150 captures the temperature of the catalyst forming the fluidized bed, the atmosphere of the reactor 105 and / or the reactor wall 105.
- the recirculator 155 is designed to compensate the pressure losses, or pressure, successively in: the preheating means 160, the reactor 105, the water separating means 125, particularly for the device 10 described with reference to FIG.
- the recirculator 155 is, for example, a fan, a booster or an ejector.
- the fluid used to produce the ejection mechanism is, for example, water vapor in partial complement or in replacement of the steam 165 of WGS occurring in the reactor 105.
- the recirculated product flow is increased to cool the reaction medium of the reactor 105. Conversely, if the sensed temperature is below the predetermined temperature, the flow rate of recirculated products is decreased.
- the device 10 comprises upstream of the inlet of the reactor 105, a means 160 for preheating the mixture at a temperature above 150 ° C.
- this preheating means 160 heats the mixture to a temperature greater than or equal to 200 ° C.
- this preheating means 160 heats the mixture to a temperature greater than or equal to 230 ° C. Preferably, this preheating means 160 heats the mixture at a temperature below 280 ° C. and preferably at a temperature below the operating temperature of the reactor 105.
- the preheating means 160 is, for example, a fluid / gas heat exchanger, or electric, configured to transmit to the mixture a temperature greater than 150 ° C.
- the temperature of the mixture is brought to a temperature greater than or equal to 230 ° C.
- the device 10 may comprise, in these embodiments, a temperature sensor 162 of the mixture downstream of the preheating means 160.
- the power supplied by the preheating means 160 varies as a function of the temperature sensed at the output of 160 and a predetermined temperature-setpoint. If the sensed temperature is higher than the set temperature, the power supplied by the preheating means 160 is reduced. Conversely, the power of the preheating means 160 is increased when the sensed temperature is below the set temperature.
- the device 10 comprises a pipe 165 for injecting water vapor into the pipe 15. supply of syngas upstream of the site of formation of the mixture between the syngas and the methanation products leaving the bypass 140.
- the injection pipe 165 is, for example, a sealed pipe connected to a device (not shown) for producing water vapor.
- This device for producing water vapor heats, for example, water separated from synthetic natural gas to produce water vapor injected into the syngas.
- the water thus injected makes it possible to carry out a WGS reaction and to limit the formation of coke in the reactor 105.
- the steam promotes, by the WGS reaction, the adjustment of the H2 / CO ratio close to the optimum conditions for the methanation reaction.
- the analysis of the prior art has shown that the WGS reaction can be carried out in a dedicated reactor located upstream of the reactor 105 or even within this reactor in parallel with the methanation reactions. In order to benefit from the economic gains and simplification of the process, the realization of the methanation and WGS reactions is preferably carried out in a single device.
- the device 10 comprises a diversion duct 170, a portion of the hot products of methanation reactions, comprising:
- the deflection conduit 170 is, for example, a sealed conduit.
- the inlet 175 is, for example, an orifice opening on the inside of the synthetic natural gas transport pipe, upstream of the water separating means 125.
- the outlet 180 is, for example, an injection orifice of the synthetic natural gas into the mixture, downstream of the preheating means 160.
- the natural synthesis gases, hot, allow to keep constant the flow in the reactor 105.
- the flow rate of the gasification syngas is entirely a function of the quantities of hydrocarbon compounds available.
- the hydrodynamic conditions must be kept as constant as possible. Nevertheless, if the available hydrocarbon material is insufficient and consequently the flow rate of syngas is decreased, it is necessary to maintain a constant overall flow rate into the reactor 105 or to opt for a very flexible technology. Even in the case of the fluidized bed capable of operating in a range of flow rates from one to six, too low flow rates can cause degradation of cooling and thus conversion.
- the flow at the outlet of the preheating means 160 is supplemented by a recirculation
- a hot recirculation fluid does not cause thermal imbalance of the reactor 105, but makes the device 10 very flexible.
- the device 10 comprises:
- a recirculator 190 a recirculator 190, products entered in the bypass line 165, the recirculator 190 being controlled according to the measured flow rate.
- the flow measurement means 185 may be of any type known to those skilled in the art that is suitable for measuring the flow of gas, such as an anemometer, a Coriolis flowmeter, a vortex flowmeter or an electromagnetic flowmeter, for example .
- the recirculator 190 is similar to the recirculator 155 in structural terms.
- the control of this recirculator 190 is performed as a function of the flow rate measured by the measuring means 185 and a predetermined flow rate value 187. If the measured flow rate is lower than a predetermined set flow 187, the recirculator 190 is actuated so as to bridge the difference between the measured flow rate and the set flow 187 by an equivalent flow rate of synthetic natural gas.
- the device 10 comprises means 145 for separating carbon dioxide from the dehydrated synthetic natural gas positioned downstream of the bypass 140.
- the implementation of the device 10 object of the present invention provides synthesis gas close to the specifications of the gas network requiring few additional operations.
- the device 10 can thus be implemented for a pressure range of between one bar and one hundred bars and a range of predetermined temperatures of between 230 ° C. and 700 ° C.
- FIG. 2 which is not to scale, shows a schematic view of a second embodiment of the device 20 of the present invention.
- This device 20 for producing synthesis gas is similar to the device 10 described with reference to FIG. 1.
- the references 205, 210, 215, 220, 225, 227, 230, 235, 240, 250, 255, 260, 262, 265, 270, 275, 280, 285, 287 and 290 of the device 20 respectively correspond to the references 105, 1 10, 1 15, 120, 125, 127, 130, 135, 140, 150, 155, 160, 162, 165, 170, 175, 180, 185, 187 and 190 of the device 10.
- the device 20 further comprises a means 245 for separating carbon dioxide from the dehydrated synthetic natural gas positioned upstream of the bypass 240.
- This separation means 245 may be positioned upstream or downstream of the water separating means 225.
- FIG. 3 shows, in the form of a logic diagram of steps, a particular embodiment of the method that is the subject of the present invention.
- This synthesis gas production process comprises:
- a methanation reaction step 305 comprising:
- a step 320 of water separation comprising:
- a step 340 for separating carbon dioxide from the dehydrated synthetic natural gas leaving the separation step 320 preferentially, a step 340 for separating carbon dioxide from the dehydrated synthetic natural gas leaving the separation step 320,
- This method 30 is implemented, for example, by a device 10 or object 20 of the present invention and described with reference to Figures 1 or 2.
- the process which is the subject of the present invention comprises, upstream of the reaction step 305, a preheating step 340.
- This preheating step 340 is carried out, for example, by a preheating means 160 or 260, as described with reference to FIGS. 1 or 2.
- FIGS. 4 to 7 are the result of simulations carried out to determine the impact of the device and method that is the subject of the present invention. These results are compared with a simulation of a recirculation case without dehydration, as is the case for example in the first stage of the boiling water reactor, for example.
- the objective of the device and method that are the subject of the present invention is also to minimize the steps of setting the specifications while operating a single-stage methanation at moderate pressure and acceptable in terms of costs. For these same reasons, the SNG is preferentially compressed at the end of the production line after the required separations for injection on the network.
- the simulations carried out and presented below were carried out at 8 bar and a methanation temperature of 320 ° C.
- Figures 4 and 5 show respectively the Wobbe index and the SNG PCS before the separation of h for the reference configuration with recirculation of the wet SNG, the recirculation of the dehydrated SNG and the recirculation of the dehydrated and decarbonated SNG.
- FIG. 4 shows, on the ordinate, the Wobbe index of the synthetic natural gas produced by the device, 10 or 20, as a function of the recirculation rate, on the abscissa, and the nature of the recirculated synthetic natural gas. at the reactor inlet, 105 or 205, methanation.
- the recirculation of dehydrated and decarbonated synthetic natural gas 415 further improves the Wobbe index of the synthetic natural gas produced by the device, even with a recirculation rate of less than one.
- FIG. 5 shows, on the ordinate, the PCS of the synthetic natural gas produced by the device, 10 or 20, as a function of the recirculation rate, on the abscissa, and on the nature of the recirculated synthetic natural gas at the inlet of the reactor, 105 or 205, methanation.
- FIG. 6 shows, on the ordinate, the relative decrease in the molar flux of hb at the outlet of the device, 10 or 20, as a function of the recirculation rate, on the abscissa, and the nature of the recirculated synthetic natural gas input.
- reactor, 105 or 205 methanation.
- the CO / hbO ratio is retained at the reactor inlet relative to the initial CO / hbO ratio for operating the reactor.
- the risk of deactivation of the coking methanation catalyst remains relatively low.
- the decarbonation upstream of recirculation of the synthetic natural gas seems more efficient in terms of molar reduction of the hb.
- a recirculation flow four to eight times greater is required in simple dehydration compared to the solution with decarbonation.
- the minimum recirculation rate necessary to avoid the separation of hb is estimated at 1, 6.
- FIG. 7 makes it possible to visualize the evolution of the normalized exothermicity of the reactor, ie the heat to be evacuated with respect to a case without recirculation, as a function of the recirculation rate for the reference configuration and the two devices, 10 and 20, described above.
- FIG. 7 shows, on the ordinate, the exothermicity of the methanation reaction of the device, 10 or 20, as a function of the recirculation rate, on the abscissa, and on the nature of the recirculated synthesis natural gas at the inlet of the reactor , 105 or 205, of methanation.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1556748A FR3038909A1 (en) | 2015-07-16 | 2015-07-16 | DEVICE AND METHOD FOR PRODUCING SYNTHETIC METHANE |
FR1650494A FR3038910B1 (en) | 2015-07-16 | 2016-01-21 | DEVICE AND METHOD FOR THE PRODUCTION OF SYNTHETIC GAS |
PCT/FR2016/051792 WO2017009576A1 (en) | 2015-07-16 | 2016-07-12 | Device and method for producing synthetic gas |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3322778A1 true EP3322778A1 (en) | 2018-05-23 |
EP3322778B1 EP3322778B1 (en) | 2020-03-25 |
Family
ID=55590046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16757688.3A Active EP3322778B1 (en) | 2015-07-16 | 2016-07-12 | Apparatus and method for producing synthesis gas |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP3322778B1 (en) |
KR (1) | KR20180030678A (en) |
CN (1) | CN107922864A (en) |
BR (1) | BR112018000922B1 (en) |
DK (1) | DK3322778T3 (en) |
FR (2) | FR3038909A1 (en) |
MY (1) | MY186992A (en) |
WO (1) | WO2017009576A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3112537B1 (en) * | 2020-07-14 | 2023-03-31 | Engie | DEVICE AND METHOD FOR THE HYBRID PRODUCTION OF SYNTHETIC DIHYDROGEN AND/OR SYNTHETIC METHANE |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3967936A (en) * | 1975-01-02 | 1976-07-06 | The United States Of America As Represented By The United States Energy Research And Development Administration | Methanation process utilizing split cold gas recycle |
DE3032123A1 (en) * | 1979-10-22 | 1981-04-30 | Conoco Inc., 74601 Ponca City, Okla. | METHOD FOR PRODUCING A METHANE-REPLACING NATURAL GAS |
CA2644457C (en) * | 2006-04-06 | 2014-07-08 | Fluor Technologies Corporation | Configurations and methods of sng production |
DK2110425T4 (en) * | 2008-04-16 | 2022-05-30 | Casale Sa | PROCEDURE AND SYSTEM FOR SYNTHETIC NATURAL GAS |
GB201019054D0 (en) * | 2010-11-11 | 2010-12-29 | Johnson Matthey Plc | Process |
GB201313402D0 (en) * | 2013-07-26 | 2013-09-11 | Advanced Plasma Power Ltd | Process for producing a substitute natural gas |
FR3012468B1 (en) * | 2013-10-28 | 2016-03-11 | Gdf Suez | DEVICE AND METHOD FOR PRODUCING NATURAL GAS SUBSTITUTION AND NETWORK COMPRISING SAME |
-
2015
- 2015-07-16 FR FR1556748A patent/FR3038909A1/en active Pending
-
2016
- 2016-01-21 FR FR1650494A patent/FR3038910B1/en active Active
- 2016-07-12 DK DK16757688.3T patent/DK3322778T3/en active
- 2016-07-12 KR KR1020187004817A patent/KR20180030678A/en unknown
- 2016-07-12 MY MYPI2018700160A patent/MY186992A/en unknown
- 2016-07-12 WO PCT/FR2016/051792 patent/WO2017009576A1/en active Application Filing
- 2016-07-12 BR BR112018000922-9A patent/BR112018000922B1/en active IP Right Grant
- 2016-07-12 EP EP16757688.3A patent/EP3322778B1/en active Active
- 2016-07-12 CN CN201680049618.4A patent/CN107922864A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
KR20180030678A (en) | 2018-03-23 |
FR3038909A1 (en) | 2017-01-20 |
BR112018000922B1 (en) | 2022-03-08 |
MY186992A (en) | 2021-08-26 |
WO2017009576A1 (en) | 2017-01-19 |
CN107922864A (en) | 2018-04-17 |
FR3038910A1 (en) | 2017-01-20 |
BR112018000922A2 (en) | 2018-09-11 |
FR3038910B1 (en) | 2020-01-10 |
EP3322778B1 (en) | 2020-03-25 |
DK3322778T3 (en) | 2020-06-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3322777B1 (en) | Device and method for producing synthetic gas | |
EP2142622B1 (en) | Method for producing a purified synthesis gas from a biomass including a purification step upstream from the partial oxidation | |
WO2008017741A1 (en) | Method of producing synthetic gas with partial oxidation and steam reforming | |
EP2802638B1 (en) | Integrated method for the chemical-looping gasification and indirect combustion of solid hydrocarbon feedstocks | |
FR2893033A1 (en) | Synthesis gas production for e.g. petrochemicals, involves performing electrolysis of water to produce oxygen and hydrogen, and subjecting stream including carbon in carbonaceous material to partial oxidation with pure oxygen | |
EP2706103B1 (en) | Method for gasification of a charge of carbonated material with improved efficiency | |
EP3322778B1 (en) | Apparatus and method for producing synthesis gas | |
FR2956656A1 (en) | PROCESS FOR THE PRODUCTION OF SYNTHESIS GAS | |
EP2782984B1 (en) | Biomethane production method | |
EP3390585A1 (en) | Process for the fluidized-bed gasification of tyres | |
EP3173459A1 (en) | Quick-pyrolysis reactor of organic particles of biomass with counter-current injection of hot gases | |
EP4182421A1 (en) | Device and method for hybrid production of synthetic dihydrogen and/or synthetic methane | |
EP3443051A1 (en) | Device and method for the cogeneration of methanol and synthesis methane | |
EP3031884B1 (en) | Method for gasifying a load of carbonaceous material with optimised material yield and production cost | |
FR3027311A1 (en) | PROCESS AND DEVICE FOR THE PYRO-GASIFICATION OF A CARBONACEOUS MATERIAL COMPRISING A FUSION ASH BATH | |
CA2861050A1 (en) | Integrated method for the chemical-looping gasification and indirect combustion of solid hydrocarbon feedstocks | |
BE494451A (en) | ||
FR3050123A1 (en) | DEVICE AND METHOD FOR CO2 HYDROGENATION TO PRODUCE METHANOL AND DEVICE AND METHOD FOR COGENERATION OF METHANOL AND SYNTHETIC METHANE | |
BE474683A (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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: 20180209 |
|
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) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20190314 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20191010 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAR | Information related to intention to grant a patent recorded |
Free format text: ORIGINAL CODE: EPIDOSNIGR71 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
INTG | Intention to grant announced |
Effective date: 20200212 |
|
AK | Designated contracting states |
Kind code of ref document: B1 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 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016032570 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1248541 Country of ref document: AT Kind code of ref document: T Effective date: 20200415 Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 Effective date: 20200530 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: NO Ref legal event code: T2 Effective date: 20200325 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200625 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200626 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200818 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200725 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016032570 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
26N | No opposition filed |
Effective date: 20210112 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200712 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200712 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: UEP Ref document number: 1248541 Country of ref document: AT Kind code of ref document: T Effective date: 20200325 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200325 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NO Payment date: 20230622 Year of fee payment: 8 Ref country code: NL Payment date: 20230622 Year of fee payment: 8 Ref country code: IT Payment date: 20230620 Year of fee payment: 8 Ref country code: FR Payment date: 20230621 Year of fee payment: 8 Ref country code: DK Payment date: 20230622 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20230620 Year of fee payment: 8 Ref country code: CH Payment date: 20230801 Year of fee payment: 8 Ref country code: AT Payment date: 20230622 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230620 Year of fee payment: 8 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20240212 |