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  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/382—Multi-step processes
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  • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
  • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
  • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
  • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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  • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
  • C01B2203/0405—Purification by membrane separation
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
  • C01B2203/0405—Purification by membrane separation
  • C01B2203/041—In-situ membrane purification during hydrogen production
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  • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
  • C01B2203/0465—Composition of the impurity
  • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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  • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
  • C01B2203/0465—Composition of the impurity
  • C01B2203/0495—Composition of the impurity the impurity being water
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/08—Methods of heating or cooling
  • C01B2203/0872—Methods of cooling
  • C01B2203/0883—Methods of cooling by indirect heat exchange
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  • C01B2203/08—Methods of heating or cooling
  • C01B2203/0872—Methods of cooling
  • C01B2203/0888—Methods of cooling by evaporation of a fluid
  • C01B2203/0894—Generation of steam
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1241—Natural gas or methane
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1258—Pre-treatment of the feed
  • C01B2203/1264—Catalytic pre-treatment of the feed
  • C01B2203/127—Catalytic desulfurisation
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1288—Evaporation of one or more of the different feed components
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/14—Details of the flowsheet
  • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
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  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/14—Details of the flowsheet
  • C01B2203/146—At least two purification steps in series
  • C01B2203/147—Three or more purification steps in series

Definitions

• the present invention relates to a process for the production of synthesis gas, implementing a reforming step in a catalytic reactor with a ceramic membrane (RCMC).
• RCMC ceramic membrane
• Synthetic gas consisting of molecules usable in refining or petrochemicals (hydrogen, carbon monoxide) and co-produced molecules
• hydrocarbons natural gas, liquefied petroleum gas or LPG, naphtha, petroleum residues
• coke coke
• this reforming is a controlled oxidation, the oxidant being water vapor, carbon dioxide, oxygen or a mixture containing at least two of the preceding oxidants.
• oxidant depends on the nature of the hydrocarbons to be reformed, the oxidants available, the H 2 / CO ratio required in the synthesis gas to satisfy, after separation and purification, the needs of the local market in hydrogen, in monoxide of carbon or as a mixture of the two constituents (synthesis gas for the synthesis of oxo alcohols for example).
• oxygen When oxygen is used as an oxidant (reforming of petroleum residues or coke, reforming of naphtha, or lighter hydrocarbons when the demand for H 2 is low), the oxygen must be made available under pressure (10 to 80 10 5 Pa) and with a high purity (greater than 95%), in order to avoid costly elimination of inert gases (nitrogen and argon) in the synthesis gas or in the processes located downstream.
• inert gases nitrogen and argon
• an oxidizing mixture also called oxidizing mixture, containing oxygen
• the ceramic membrane used is a mixed conductor, both ionic and electronic and has the particularity when it is subjected to a partial pressure difference of oxygen to let the O 2 " ions pass through a mechanism of diffusion of the ions through oxygen vacancies contained in the structure of the ceramic.
• the oxygen molecules are first ionized then the ions diffuse at through the oxygen vacancies; the oxygen ions are then de-ionized and the oxygen molecules react with the hydrocarbon molecules to generate synthesis gas.
• a catalyst for example based on Ni allows a very rapid reforming reaction and almost total depletion of oxygen, on the hydrocarbon charge side.
• the diffusion of oxygen ions through the mixed ceramic membranes is only effective at a sufficiently high temperature, typically above 500 ° C. and the operating temperature must be even higher, typically above 700 ° C., in order to obtain a significant oxygen flow; the flows of oxygen ions through these ceramic membranes vary greatly with temperature and can have an exponential temperature dependence, according to Arrhenius' law.
• the catalytic reactor with ceramic membrane can be of planar, tubular or monolithic configuration, it is preferably of tubular or monolithic configuration to offer sufficient mechanical strengths.
• Mixed conductive ceramic membranes can be self-supporting or present on porous supports to obtain higher oxygen flows.
• US Pat. No. 6,077,323 is known for a synthesis gas production process, implementing a RCMC in which the hydrocarbon feedstock feeding the process is a mixture of gaseous hydrocarbons rich in methane to which one or more of the following constituents are optionally added: water, carbon dioxide, hydrogen, to form the feed gas for the RCMC.
• the mixture of gaseous hydrocarbons is desulphurized but not pre-reformed before being introduced in the RCMC at a temperature between 510 ° C and 760 ° C, this temperature depending on the composition of the mixture.
• the oxidizing mixture supplying the RCMC is preheated to a temperature not exceeding that of the feed gas supplying the RCMC by more than 111 ° C.
• the oxidizing mixture leaving the reactor also called oxygen-depleted mixture or depleted mixture, presents at the outlet of the RCMC a temperature higher than that of the oxidizing mixture at the inlet of the RCMC.
• the oxygen recovery rate in the oxidizing mixture feeding the RCMC is greater than or equal to 90%.
• the subject of the invention is a process for the production of synthesis gas containing hydrogen and carbon monoxide using:
• RCMC ceramic membrane
• the method of the invention may include one or more of the following characteristics, taken alone or in any technically possible combination:
• step (a) The mixture of hydrocarbons from step (a) is brought to a temperature at least 111 ° C lower than that of the oxidizing mixture.
• the preheating of the oxidizing mixture to a higher temperature contributes to compensating for the endothermic effect of the reforming in the inlet zone of the RCMC and in maintaining in this zone the temperature of the membrane at a level compatible with a high permeability and reduces the size of the RCMC and the corresponding investment.
• Step (a) is carried out in a catalytic reactor at a temperature between 450 and 550 ° C, said reactor preferably being of the adiabatic type and the mixture of hydrocarbons intended for its supply is preheated to a temperature of 500 ° vs.
• the process can treat a mixture which may be natural gas, refinery or petrochemical waste gas, liquefied petroleum gas, naphtha, or any mixture of these different sources, containing methane and heavier hydrocarbons in all proportion.
• a mixture which may be natural gas, refinery or petrochemical waste gas, liquefied petroleum gas, naphtha, or any mixture of these different sources, containing methane and heavier hydrocarbons in all proportion.
• the depleted mixture at the outlet of step (b) is at a temperature lower than that of the oxidizing mixture feeding step (b), and the temperature difference is preferably at least equal to 75 ° C.
• the oxidizing mixture is a heat vector for the benefit of the RCMC.
• the temperature of the mixture of hydrocarbons before step (b) is between 550 and 760 ° C, preferably 650 ° C, this being a function of metallurgical constraints.
• the raw synthesis gas leaving the RCMC is at a temperature between 800 ° C and 1100 C C, and the temperature of the depleted mixture is lower than that of said synthesis gas.
• the method implements steps of cooling, separation and / or purification and / or treatment of the raw synthesis gas from step (b).
• the raw synthesis gas is cooled by any means making it possible to recover the sensible heat available, and preferably a boiler for the production of water vapor, an exchanger incorporating a reforming catalyst. It is then cooled by a counter-current exchange with one or more fluids such as the mixture of hydrocarbons, boiler water, demineralized water, and optionally by heat exchange with the gas treatment modules. synthesis located downstream. It is then treated according to the specifications requested by the market in purification and separation modules for its various constituents, such as at least one decarbonation module by washing, and / or at least one H ratio adjustment module. 2 / CO by permeation, and / or at least one module for the purification of hydrogen by selective adsorption.
• the oxidizing mixture feeding step (b) is obtained by treatment of an initial oxygenated gas mixture containing from 10 to 50 mol% of oxygen.
• the mixture can also contain, without limitation, water vapor, carbon dioxide and inert materials such as nitrogen and argon.
• the mixture can in particular be air, enriched air coming from nitrogen production units, gas coming from combustions operating with a large excess of air, combustion gas feeding one (or coming from) gas turbine, or a mixture of these gases.
• the means used to transfer the heat during all or part of the steps for preheating the various fluids of the process comprise at least one preheating oven using the heat contained in the depleted mixture, and said oven is also provided with at least an afterburner.
• the various process fluids are understood to mean in particular: make-up demineralized water, boiler water, the initial oxygenated mixture, the mixture of hydrocarbons at the various stages of the process.
• the preheating stages also include the stages of production and superheating of steam, as well as those of vaporization of liquid hydrocarbons.
• the post combustion is advantageously supplied with heating gas and possibly with initial oxygenated gas to meet all of the preheating, vaporization and heating needs of the various process fluids and to be able to control its overall power independently of the operation of the reactor.
• the oxidizing mixture is obtained by preheating the initial oxygenated gas mixture by heat exchange with the depleted mixture in a preheating oven and / or by direct combustion of so-called primary heating gas and depletion of said initial oxygenated gas mixture in at least one combustion chamber.
• the heating gas used is preferably the waste gas or gases generated by the downstream treatment modules for the raw synthesis gas which can be supplemented by the modules that use the synthesis gas, and / or any fuel available near the unit.
• the initial oxygenated gas is all or part of the combustion gas available at the outlet of a gas turbine present on site, under a pressure of less than 2 10 s Pa (absolute) and at a temperature between 500 and 600 ° C.
• the oxidizing mixture feeding step (b) is all or part of the combustion gas available at the outlet of the combustion chamber of a gas turbine associated with the unit, under a pressure between 20 and 50 10 ⁇ Pa abs. and at a temperature between 1100 ° C and 1300 ° C. advantageously, the depleted mixture at the outlet of step (b) feeds the gas turbine for the co-production of electrical energy.
• the depleted mixture at the outlet of the gas turbine feeds the preheating oven.
• the mixture of pre-reformed hydrocarbons feeds step (b) at a pressure which does not differ by more than 10% from the pressure of the oxidizing mixture feeding said step (b).
• the oxidizing mixture supplying step (b) is formed by all or part of a first combustion gas available at the outlet of a first combustion chamber supplied by a first fraction of combustible gas and by a first oxygenated gas, for example the combustion air available at the discharge of the air compressor of an associated gas turbine.
• the oxidizing mixture is available at a pressure between 20 and 50 10 ⁇ Pa abs. and at a temperature between 871 and 1100 ° C.
• the mixture of pre-reformed hydrocarbons feeds step (b) at a pressure which does not differ by more than 10% from that of the oxidizing mixture.
• the depleted mixture at the outlet of step (b) is mixed with the unused part of the first combustion gas to supply a second combustion chamber also supplied with a second part of combustible gas.
• the second combustion gas from the second combustion chamber is available at a pressure between 20 and 50 10 6 Pa abs. and at a temperature between 1100 and 1300 ° C, independent of the operating temperature of the RCMC.
• the second combustion gas from the second combustion chamber is preferably expanded in the gas turbine to produce electricity.
• the combustion gas from the gas turbine advantageously feeds the preheating oven.
• the initial oxygenated gas is all or part of the waste gas from a unit for producing nitrogen from air, containing 25 to 40 mol% of oxygen, made available under a pressure higher than 1.6 10 ⁇ Pa abs and at room temperature.
• Figure 1 shows schematically the different stages of a process for the simultaneous production, from natural gas, high purity hydrogen and H 2 / CO mixture which can be used for the synthesis of oxo alcohols.
• FIG. 2 represents a preheating module essentially comprising a preheating oven and a combustion chamber intended for the implementation of the invention
• Figure 3 shows a first variant of the preheating module incorporating an associated gas turbine.
• Figure 4 shows a second variant of integration of a gas turbine for the implementation of the preheating unit according to the invention.
• Figure 5 shows a third variant of integration of a gas turbine for the implementation of the preheating unit according to the invention.
• Figure 6 shows another variant of the preheating module according to the invention, using a waste gas from a nitrogen production unit present on site.
• the mixture of hydrocarbons supplying the process consists of natural gas called GN, which, after addition of hydrogen, is preheated to a temperature of approximately 400 ° C. in the preheating module 1 and is desulfurized by a conventional means 2 comprising a hydrogenation reactor for sulfur compounds and at least one reactor for removing hydrogen sulfide on a zinc oxide bed.
• a conventional means 2 comprising a hydrogenation reactor for sulfur compounds and at least one reactor for removing hydrogen sulfide on a zinc oxide bed.
• the desulfurized natural gas is preheated to a temperature of approximately 500 ° C. and is pre-reformed in an adiabatic reactor 3 containing a nickel-based catalyst.
• the pre-reformed mixture a mixture of methane, hydrogen, carbon monoxide, carbon dioxide and water, is preheated to 650 ° C; it is introduced into reactor 4 - catalytic reactor with ceramic membrane or RCMC.
• the preheating steps which, with the exception of the first of them, are not represented in FIG. 1, are carried out in the associated preheating module (a representation of this module is described below with FIG. 2) .
• Air called AP is used as the initial oxygen mixture, it is compressed in a compressor 5 at a pressure sufficient to compensate for the pressure drops in the oxidizing mixture circuit, then is preheated to approximately 1000 ° C before feeding the RCMC .
• This preheating is carried out in the associated preheating module described in Figure 2.
• the oxidizing mixture called MO is obtained, which is introduced into the RCMC.
• the oxidizing mixture MO is depleted in oxygen by yielding part of this oxygen by permeation through the ceramic membrane.
• the depleted MA mixture available at the outlet of RCMC is at a temperature of 925 ° C., and has a residual oxygen content of approximately 2%.
• the heat available in the MA mixture is then used in the preheating module.
• a crude synthesis gas called GS product of the reforming of GN by the oxygen extracted from the oxidizing mixture MO through the ceramic membrane and by the water present in the pre-reformed gas, is obtained at the outlet of the RCMC.
• the synthesis gas GS yields its sensible heat in a boiler 6 generating steam in excess quantity compared to the needs of the unit. It is then cooled in 7 by heat exchange with boiler water and demineralized water, treated in a decarbonation module 8 to remove carbon dioxide, then passes through a drying module 9 to remove the water.
• the GS gas is then treated in a permeation module 10 to extract part of the hydrogen through a polymer membrane and thus produce a mixture with an H 2 / CO ratio close to 1, an optimal ratio for feeding a hydroformylation reactor. and for the final production of oxo alcohols.
• the hydrogen recovered in the permeate of the polymer membrane is used to regenerate the adsorbents of the drying module 9 and then compressed in a compressor 11 to feed a selective adsorption module 12 on adsorbents (commonly called PSA module) which allows the production of high purity hydrogen.
• PSA module a selective adsorption module 12 on adsorbents
• the preheating module essentially comprises a preheating oven and a combustion chamber, it is now described according to several variants with reference to Figures 2 to 6.
• Figure 2 shows a preheating module in which the primary air AP intended to generate the oxidizing mixture MO is compressed in an air compressor 5 at a pressure of approximately 2 10 s Pa abs, it is preheated to approximately 450 ° C in the preheating furnace 101, it is then superheated in a combustion chamber 102 to approximately 1000 ° C. by direct combustion of heating gas preferably consisting of the combustible residue from the PSA module and an additional heating gas available on the site, GC.
• heating gas preferably consisting of the combustible residue from the PSA module and an additional heating gas available on the site, GC.
• the oxidizing mixture MO feeds the RCMC 4.
• the depleted mixture MA is at a temperature of the order of 925 ° C. and has a residual oxygen content of approximately 2 mol%; this corresponds to an oxygen extraction rate in the RCMC reactor of 87.5%.
• the heat available in the MA mixture supplemented by that of an afterburner using an additional secondary GC heating gas and an additional secondary air makes it possible to satisfy all of the unit's needs, namely in particular:
• FIG. 3 shows a variant of the preheating module in which all or part of the primary air AP intended to generate the oxidizing mixture MO is replaced by all or part of the effluent available at the outlet of a gas turbine 201, under a pressure less than 210 S Pa abs, at a temperature between 450 ° and 700 ° C and which typically contains between 10 and 15% oxygen.
• the effluent from the gas turbine is then superheated in the combustion chamber 202 associated with approximately 1000 ° C. by direct combustion of heating gas preferably consisting of the combustible residual from the PSA module and an additional heating gas available on the site, GC.
• the oxidizing mixture MO feeds the RCMC 4.
• the mixture MA is at a temperature of the order of 925 ° C. and has a residual oxygen content of approximately 2 mol%; this corresponds to an oxygen extraction rate in the RCMC of between 71% and 84%; the heat available in MA, supplemented by that of an afterburner using an additional secondary GC heating gas and a secondary air addition supplies the preheating furnace 203 and makes it possible to satisfy all of the unit's needs, at know in particular:
• Figure 4 shows a variant of the preheating module in which the RCMC 4 is supplied directly with all or part of the combustion gas available at the outlet of the combustion chamber 301 of a gas turbine 302, under a pressure of between 10 and 25 10 s Pa abs, at a temperature between 871 and 1300 ° C, this combustion gas constituting an oxidizing mixture MO containing from 10 to 15 mol% of oxygen.
• the RCMC 4 works in this case under pressure.
• the depleted oxidizing mixture MA is at a pressure between 9 and 24 10 s Pa abs.
• the depleted oxidizing mixture MA is then expanded in the gas turbine 302, coupled to the associated air compressor and to an electric energy generator.
• the effluent available at the output of the turbine under a pressure of 1.2 to 10 ⁇ Pa abs., Feeds the preheating furnace 305, after addition of a post-combustion fuel using the residual PSA module, a secondary heating gas side and a secondary air make-up. This makes it possible to satisfy all of the unit's needs, namely in particular:
• FIG. 5 shows a variant of the preheating unit in which the oxidizing mixture MO supplying the RCMC 4 consists of all or part of the combustion gas available at the outlet of a first combustion chamber 401 under a pressure of between 10 and 25 bars abs., at a temperature between 871 and 1100 ° C., MO containing from 10 to 15 mol% of oxygen.
• This first combustion chamber is supplied with a primary heating gas and with combustion air taken off at the outlet of the compressor 404 coupled to a gas turbine 403.
• the depleted mixture MA is at a pressure between 9 and 24 bars abs., At a temperature between 800 and 1000 ° C and contains between 2% and 7 mol% of oxygen, which corresponds to an oxygen extraction rate of between 30 and 87%.
• the depleted mixture MA is then superheated in a second combustion chamber 402 at a temperature in the region of 1200 ° C. and expanded in the gas turbine.
• the effluent, available under a pressure of less than 1.2 bar abs. feeds the preheating oven 405, and after adding an afterburner using the combustible residue of the unit's PSA module, a secondary heating gas addition and a secondary air addition, makes it possible to satisfy all of the needs of the unit, namely in particular:
• FIG. 6 presents a variant of the preheating unit in which the air supplying the synthesis gas production unit is air enriched in oxygen, and is in particular the residue from a nitrogen production unit, containing between 25 and 40 mol% of oxygen.
• This enriched air, or enriched primary air is preferably made directly available at a pressure greater than 1.6 10 s Pa abs. It is preheated to around 450 ° C in the preheating oven 501, then is overheated in a combustion chamber 502 to a temperature preferably of the order of 1000 ° C by direct combustion of heating gas, preferably consisting of the combustible waste of the PSA module and an additional heating gas available on site and thus forms the oxidizing mixture MO.
• the oxidizing mixture which has an oxygen content of between 20 and 35 mol% approximately, then feeds the RCMC.
• the depleted mixture is at a temperature of 915 ° C. and has a residual oxygen content of approximately 2 mol%; this corresponds to an oxygen extraction rate in the RCMC reactor of between 90 and 95%; the heat available in the depleted mixture supplemented by the heat from an afterburner using an additional secondary heating gas and an additional secondary air makes it possible to meet all of the unit's needs, namely in particular:

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