WO2025103631A1 - Procédé et installation de production de méthanol - Google Patents

Procédé et installation de production de méthanol Download PDF

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Publication number
WO2025103631A1
WO2025103631A1 PCT/EP2024/074641 EP2024074641W WO2025103631A1 WO 2025103631 A1 WO2025103631 A1 WO 2025103631A1 EP 2024074641 W EP2024074641 W EP 2024074641W WO 2025103631 A1 WO2025103631 A1 WO 2025103631A1
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synthesis gas
reaction process
reactor
methanol
temperature
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English (en)
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Henning Schramm
Markus Kinzl
Rüdiger Schneider
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Siemens Energy Global GmbH and Co KG
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Siemens Energy Global GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
    • C01B3/12—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1838—Autothermal gasification by injection of oxygen or steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/046—Reducing the tar content

Definitions

  • the present invention relates to a process for producing methanol and a plant for producing methanol.
  • the carbon dioxide or carbon monoxide required for methanol synthesis is provided, for example, in a synthesis gas that is produced by upstream combustion or gasification of biomass, which is also referred to as the combustion route or gasification route.
  • the combustion exhaust gas therefore consists essentially of carbon dioxide and water.
  • hydrogen is added to the combustion exhaust gas.
  • reaction equation (3) Due to the high carbon dioxide content resulting from combustion—see reaction equation (3)—the water content produced in methanol synthesis according to the above reaction equation (1) must be significantly reduced in a downstream distillation stage in order to provide methanol with a certain degree of purity for fuel production. Providing and operating the distillation stage is technically complex and cost-intensive.
  • the gasification route can be chosen.
  • methanol synthesis is preceded by gasification of biomass under an oxygen deficiency or oxygen deficiency.
  • the gasification produces a gasification exhaust gas or a synthesis gas consisting of carbon monoxide, carbon dioxide, and hydrogen according to the following reaction equation (4):
  • the advantage of the gasification route is that less water is produced than the combustion route, which has to be separated by distillation.
  • combustion is a much more robust process than gasification.
  • biomass with low or heterogeneous quality can be easily converted by combustion, whereas the gasification route requires a biomass reactant with a comparatively high or constant quality.
  • CO 2 + H 2 ⁇ -> CO + H 2 0 can be designed particularly favorably to increase the carbon monoxide content in the synthesis gas and to reduce the carbon dioxide content in the synthesis gas.
  • the reaction equation (5) is sometimes abbreviated below as "RWGS reaction”.
  • the separation of unwanted carbon dioxide from the synthesis gas is no longer necessary.
  • the carbon dioxide can be converted into the carbon monoxide required for methanol synthesis, thus increasing the carbon yield from the biomass used in the first reaction process.
  • the invention is based , among other things , on the idea of reducing proportions of undesirable components in the synthesis gas by means of an endothermic reaction and , at the same time , carrying out this endothermic reaction in a simple manner using process heat from adjacent reaction processes .
  • the second temperature which is also referred to here as the RWGS temperature
  • the RWGS temperature only needs to be greater than 400 °C
  • process heat from the first reaction process or process heat from methanol synthesis can be easily used for the endothermic RWGS reaction.
  • the advantages mentioned above can be achieved, for example increasing the carbon yield or saving the distillation step, while no significant additional energy expenditure is required to carry out the RWGS reaction.
  • the effects of saving the distillation step or increasing the carbon yield clearly outweigh the costs required to carry out the RWGS reaction in the overall balance.
  • the aforementioned achievable reduction of carbon dioxide in the synthesis gas allows more heat to be generated in the methanol synthesis, since the reaction enthalpy of the reaction equation (2) CO + 2H 2 CH 3 OH is higher than the reaction enthalpy of the reaction equation (1) CO 2 + 3H 2 CH 3 OH + H 2 O.
  • more process heat is available without additional expenditure. available for further use, which can further improve the overall balance.
  • the lifespan or service life of the methanol synthesis catalyst can be increased because there is less or no water in the methanol synthesis compared to the prior art.
  • the first reaction process can comprise gasification of the biomass with oxygen and steam, the synthesis gas produced containing carbon monoxide and hydrogen.
  • the first reaction process can be gasification of the biomass.
  • the first reaction process can be a thermo-chemical conversion of the biomass into the synthesis gas containing carbon dioxide.
  • a gasification parameter known to those skilled in the art as the excess air number can be greater than zero and less than one.
  • the first reaction process takes place with an oxygen deficiency or oxygen shortage.
  • the first reaction process is gasification without subsequent combustion.
  • the resulting synthesis gas can contain carbon monoxide and hydrogen in addition to carbon dioxide.
  • the carbon dioxide content of the gasification route is lower than that of the combustion route. This means that less carbon dioxide needs to be converted in the second reaction process, and less hydrogen needs to be added.
  • the first reaction process may comprise a combustion of the biomass with oxygen, wherein the synthesis gas produced contains water.
  • the first reaction process may comprise the combustion of the biomass, i.e. a so-called oxy-combustion or oxy- Combustion of the biomass.
  • the first reaction process can be the combustion process that results directly from the ignition of gases escaping from the biomass.
  • the excess air number of the first reaction process i.e., the oxy-combustion
  • the first reaction process takes place in excess oxygen.
  • the first reaction process is combustion, which is naturally preceded by the release of a flammable gas from the biomass.
  • the first reaction process can involve biomass combustion, a wide variety of different biomass reactants of varying quality or varying degrees of homogeneity can be converted into synthesis gas in the first reaction process. This allows for simple and robust process control of the first reaction process.
  • the first reaction process can be carried out in the form of gasification in a gasification reactor and additionally in the form of combustion in a combustion reactor, wherein the synthesis gas produced in the gasification and the synthesis gas produced in the combustion are combined before the methanol synthesis is carried out.
  • the gasification, the combustion and the methanol synthesis can take place in a Y-scheme.
  • the second reaction process can be carried out after the aforementioned combining, i.e. after the node of the Y-scheme. In this way, the first reaction process can be operated simultaneously in two different variants, while only one RWGS reactor is required. Thus, a greater variety of biomass reactants can be processed while saving on an additional RWGS reactor.
  • the second temperature can be at most 300 Kelvin lower than the first temperature.
  • the first temperature can be in the form of a combustion
  • the first temperature for combustion of the biomass may be 1000 °C
  • the second temperature in the form of the RWGS temperature is at least 700 °C.
  • the first temperature in the form of a gasification temperature may be 500 °C
  • the second temperature in the form of the RWGS temperature is kept at 400 °C.
  • the first temperature can be between 700 and 1100 °C and the second temperature between 380 and 1100 °C. Due to the comparatively high first temperature in the range of 700 and 1100 °C, a high quality of the synthesis gas to be produced can be achieved, i.e. a high proportion of desired short-chain gaseous carbon compounds, in particular carbon dioxide in the case of combustion, or carbon monoxide and carbon dioxide in the case of gasification. Furthermore, the comparatively high first temperature of the exothermic first reaction provides a high potential for usable process heat.
  • a purification stage for cleaning the exhaust gas or synthesis gas generated by the first reaction process can be dispensed with if the gas is of high quality, i.e., the proportion of undesirable by-products, such as tar or wood condensate, is low.
  • the integration of an RWGS catalyst into an exhaust line of the first reaction process can be carried out particularly easily.
  • the RWGS reaction can be carried out in a comparatively wide temperature range, i.e. with a range of 720 Kelvin in the range of 380-1100 ° C.
  • the RWGS reaction can be carried out at medium temperatures around 450 °C, significantly lower than the first temperature, and thus spatially decoupled from the first reaction. Due to the large temperature difference, the exothermic first reaction process can still provide process heat for the RWGS reaction despite spatial decoupling.
  • temperatures below 350 ° C are referred to as low, temperatures above 750 ° C as high, and temperatures in between as medium.
  • the second temperature can be at least 80% of the first temperature.
  • the second temperature can be 80%, 90%, 110% or 120% of the first temperature or any value in between.
  • the first and second temperatures can differ from each other by a maximum of 20%. If the second temperature is 80-100% of the first temperature, the RWGS reaction can be easily spatially coupled with the first reaction process, for example by integrating the RWGS catalyst into an exhaust gas line which is designed to discharge the synthesis gas produced from the first reaction process. In this way, the first and second reaction processes can be carried out equally at very high temperatures, for example around 1000 °C.
  • carrying out the first reaction process can comprise discharging the generated synthesis gas via an exhaust line, wherein carrying out the second reaction process is integrated into the discharging of the generated synthesis gas.
  • an RWGS catalyst can be arranged in the exhaust line of the first reaction process. In this way, the temperature difference between the first and second reaction processes can be kept very small.
  • the process can comprise the following step: supplying hydrogen, in particular in the form of a hydrogen surplus, on the reactant side of the second reaction process.
  • additional hydrogen is provided as a reactant for the RWGS reaction, in particular more hydrogen than can typically be converted with the synthesis gas produced in the RWGS reaction.
  • the RWGS reaction equilibrium is influenced in favor of the desired products.
  • a very high or even complete conversion of carbon dioxide can thus occur in the RWGS reaction.
  • oxide and hydrogen to form carbon monoxide and water can be reduced to less than 1%.
  • the method may comprise the following steps:
  • the synthesis gas can be purified before it reaches the RWGS catalyst, while at the same time, the process heat from the first reaction process can be used to carry out the RWGS reaction.
  • the first reaction can take place at a high temperature of 800-1000 °C, and the purification can take place at a purification temperature in the range of 30-350 °C. Thanks to a high first temperature, the purified synthesis gas can be heated to an RWGS temperature of 400 °C, 600 °C, or 750 °C, for example, depending on the investment required for the design of the recuperator heat exchanger.
  • the procedure may include the following
  • Steps include: Extraction of process heat from the first reaction process and supplying the extracted process heat to the second reaction process. These steps enable the utilization of the process heat of the first reaction process if the RWGS reaction is carried out spatially decoupled from the first reaction process.
  • the method may comprise the following steps:
  • Methanol synthesis for example, can be carried out using the well-known low-pressure process, i.e., at a pressure of 50 to 100 bar and a temperature of 200 to 300 °C.
  • the first and second reaction processes can each take place at a comparatively low pressure of 1 to 15 bar. Cooling the synthesis gas to, for example, 40 °C allows the required compression of the cooled synthesis gas to be carried out economically, for example, to a synthesis pressure of 80 bar.
  • any water present in the synthesis gas particularly as a result of biomass combustion, can be condensed out and separated particularly easily.
  • the volume flow of the gas to be compressed is reduced considerably. This reduces the energy required for compression and the equipment required to provide a compressor as needed.
  • carrying out the methanol synthesis can comprise a synthesis loop for producing crude methanol, wherein the crude methanol produced contains 90.0 to 99.5% methanol and a maximum of 10.0% water.
  • carrying out the methanol synthesis can be carried out without methanol distillation for separating water from the crude methanol.
  • the synthesis loop is understood to be that process section or plant component of a methanol synthesis process or methanol synthesis plant in which the reactants hydrogen and carbon monoxide and/or carbon dioxide react to form methanol or crude methanol. Conventionally, the resulting water is separated from the crude methanol in a subsequent methanol distillation to obtain pure methanol.
  • a plant for producing methanol comprises a first reactor for producing a synthesis gas containing carbon dioxide, set up for gasifying biomass and/or for burning biomass, the first reactor having an exhaust gas line for discharging the synthesis gas produced, and a second reactor in the form of a reverse water gas shift reactor, the second reactor, in particular a catalyst of the second reactor, being arranged within the exhaust gas line and adjacent to the first reactor.
  • the RWGS reactor in particular the RWGS catalyst, is arranged within the exhaust line and adjacent to the first reactor, the temperature gradient between the gasification or combustion, i.e., the first and second reaction processes described above, and the RWGS reactor can be greatly reduced.
  • the endothermic RWGS reaction can be carried out particularly easily using the process heat of the exothermic first reaction process.
  • the plant comprises a first reactor for producing a synthesis gas containing carbon dioxide, designed for gasifying biomass and/or for burning biomass, wherein the first reactor has an exhaust gas line for discharging the carbon dioxide produced, a second reactor in the form of a reverse water gas shift reactor, a recuperator heat exchanger and a purification column.
  • the purification column is arranged between the first and second reactors and is fluidically connected thereto.
  • the recuperator heat exchanger is designed to have an outlet line- device of the first reactor with an inlet line of the second reactor in a heat-transfer manner.
  • the purification column arranged between the first and second reactors, unwanted by-products, such as tars or wood condensate, can be separated from the synthesis gas produced in the first reactor, significantly increasing the service life of the second reactor, particularly its RWGS catalyst.
  • the process heat from the exothermic first reaction process can be used to heat the purified synthesis gas, allowing the endothermic second reaction process to be carried out without additional energy expenditure, even if the first and second reactors are spatially decoupled due to the interposed purification column.
  • Figure 1a is a flow diagram of a process for producing methanol according to a first embodiment
  • Figure lb, c j e an embodiment of a system for carrying out the method
  • Figure 2a is a flow diagram of a process for producing methanol according to a further embodiment
  • Figure 2b shows an embodiment of a plant for producing methanol
  • Figure 3a is a flow diagram of a process for producing methanol according to a further embodiment
  • Figure 3b shows another embodiment of a plant for producing methanol
  • Figure 4 shows a further embodiment of a system for carrying out the method.
  • Figure 1a shows a schematic flow diagram of a method for producing methanol according to a first exemplary embodiment.
  • Figures 1b and 1c show corresponding exemplary embodiments of a plant for carrying out the method.
  • a first reaction process is first carried out S10 at a first temperature TI.
  • the first reaction process uses biomass and oxygen to produce an exhaust gas containing carbon dioxide, which is also referred to herein as the synthesis gas produced.
  • the first reaction process can, for example, be technical biomass gasification or biomass combustion in the form of so-called oxy-combustion.
  • the first reaction process can be any other form of exothermic biomass utilization that produces a synthesis gas containing carbon dioxide.
  • a second reaction process S20 is carried out in the form of a reverse water-gas shift reaction at a second temperature T2 using the generated synthesis gas.
  • the person skilled in the art can select a suitable RWGS catalyst so that the RWGS reaction increases the carbon monoxide content in the synthesis gas according to the following reaction equation (5):
  • RWGS catalysts achieve this starting at a second temperature T2, i.e. an RWGS temperature, of 400°C.
  • step S21 an excess of hydrogen is fed to the RWGS reaction, whereby the amount of excess is determined by the carbon dioxide content of the synthesis gas produced in the first reaction, taking into account the above RWGS reaction equation.
  • step S30 the synthesis gas modified by the RWGS reaction, i.e. the synthesis gas with an increased carbon monoxide and reduced carbon dioxide content compared to the synthesis gas resulting directly from the first reaction process, is cooled.
  • the cooling step S30 includes a targeted condensation S32 of water, which is separated from the cooled synthesis gas in a further step S35. After cooling S30, the cooled synthesis gas is compressed S40, followed by performing a methanol synthesis S50 using the synthesis gas to produce methanol.
  • Steps S10, S20, and S30 can be carried out at a pressure between 1 and 15 bar, whereby the pressure can assume any value in between, regardless of the prevailing reaction temperature.
  • Cooling S30 cools the synthesis gas to a temperature between 20°C and 100°C, for example, 30°C, 40°C, or 50°C.
  • the pressure in the second reaction process should be at least within the stated limits of 1-15 bar can be variably adjusted without negatively affecting the second reaction process, i.e. without negatively affecting the desired reduction in the carbon dioxide content in the synthesis gas.
  • the pressure in the second reaction process can be aligned with the pressure of the first reaction process, in particular, it can have essentially the same value. In this way, the integration of an RWGS catalyst into an exhaust line of the first reaction process can be carried out particularly easily.
  • the cooled synthesis gas is brought to the pressure required for methanol synthesis, for example a pressure between 50 and 100 bar for carrying out the known low-pressure process for methanol synthesis in step S50.
  • Fig. 1b shows a plant 1 that is set up to carry out the process according to the gasification route.
  • Fig. 1c shows a corresponding plant 1 for the combustion route.
  • the plant 1 comprises a first reactor 10 in the form of a gasification reactor 10 having an exhaust line 11 in which an RWGS catalyst 20 is arranged or integrated.
  • the RWGS catalyst 20 integrated into the exhaust line thus takes over the function of the second reactor 20, i.e. the RWGS reactor 20.
  • a cooling stage 30 for cooling S30, a compressor 40 for compressing S40 and a synthesis loop 50 for carrying out S50 the methanol synthesis are connected successively downstream to the exhaust gas line 11.
  • the system 1 further comprises a supply line 21 for supplying S21 of hydrogen, wherein the supply line 21 can be arranged in the flow direction upstream or downstream of the RWGS catalyst 20 according to the embodiment shown in Fig. 1b.
  • the flow direction of the system 1 is oriented essentially from left to right in the present figures and using the arrow directions of the synthesis gas, which is abbreviated to SynGas in the figures.
  • the plant 1 shown in Fig. 1c basically corresponds to the plant 1 shown in Fig. 1b with the difference that the first reactor 10 is in the form of a combustion reactor for carrying out S10 an oxy-combustion of biomass under an oxygen excess.
  • the synthesis gas generated by combustion is discharged from the first reactor 10 via the exhaust line 11, with the RWGS catalyst being arranged in the exhaust line 11.
  • hydrogen is supplied S21 upstream of the RWGS catalyst 20, i.e., between the first reactor 10 and the RWGS catalyst 20.
  • a further supply S21 of hydrogen can be carried out downstream of the RWGS catalyst 20 (not shown in Fig. 1c).
  • FIG. 2a schematically shows a flow diagram of a method for producing methanol according to a further exemplary embodiment, in which the synthesis gas generated by the first reaction process S10 and modified by the second reaction process S20 is purified before cooling S30.
  • the synthesis gas which in the second reaction process has a second temperature T2 greater than 400°C, for example around 700°C, is first cooled in a cooling step S13 to a purification temperature T3 in the range 250-350°C.
  • the purification temperature T3 is selected such that a high proportion of the components to be separated in the purification step, such as tars or wood condensate, are separated or condensed out of the synthesis gas.
  • the synthesis gas is cooled to the purification temperature T3 and cleaned S14, for example by separating the separated or condensed components from the synthesis gas. This is followed by the Cooling S30, compression S40 and methanol synthesis S50, as described in the above embodiments.
  • FIG. 2b schematically shows a plant 1 configured to carry out the process illustrated in Fig. 2a.
  • the first reactor 10 can be a gasification reactor and/or a combustion reactor. If the first reactor 10 is a pure combustion reactor, hydrogen is fed into the exhaust gas line 11 via the feed line 21 upstream of the RWGS catalyst 20.
  • the RWGS catalyst 20 is each integrated into the exhaust gas line 11 of the first reactor 10.
  • the pressure and temperature conditions in the RWGS catalyst 20 are similar to those in the first reactor 10.
  • the first reactor can be operated at any pressure between 1 and 15 bar and have a first temperature TI greater than 400 °C.
  • the first temperature TI is greater than 750 °C.
  • the second temperature T2 is only slightly lower than the first temperature TI, for example at most 50 Kelvin lower, as shown in Figs. 1b, 1c and 2b. In this way, no additional heat energy is required to carry out S20 the second reaction process.
  • a particulate filter (not shown) can optionally be provided in the first reactor 10 and/or in the exhaust line 11 upstream of the second reactor 20 in order to reduce the particulate load for the RWGS catalyst 20 and to increase its service life.
  • Figure 3a shows a schematic flow diagram of a process for producing methanol according to a further embodiment.
  • Figure 3b shows a schematic diagram of a plant 1 which is designed to carry out the process shown in Fig. 3a. to carry out .
  • the synthesis gas produced by means of the first reaction process in step S 10 is first discharged from the first reactor 10 via the exhaust gas line 11 , S 11 .
  • the still hot synthesis gas is then passed through a recuperator heat exchanger 16 , S 12 .
  • the synthesis gas is then fed to a cleaning column 12, 13 , where it is first cooled to a cleaning temperature T3 , S 13 , and cleaned , S 14 .
  • undesired by-products such as tars and wood condensate, are separated from the synthesis gas.
  • the purified synthesis gas is then fed via an inlet line 17 to the second reactor 20 for carrying out S20 the second reaction process, S17, wherein the inlet line 17 is guided through the recuperator heat exchanger 16, so that the recuperator heat exchanger 16 couples the outlet line 11 of the first reactor 10 to the inlet line 17 of the second reactor 20 in a heat-transfer manner.
  • the purified synthesis gas is heated S16 from the low purification temperature T3 to the medium or high second temperature T2.
  • the method may additionally comprise the following steps: extracting S22 process heat from the first reaction process and supplying S24 the extracted process heat to the second reaction process.
  • the system 1 may comprise a heat transfer device 22 configured to carry out steps S22 and S24.
  • the provision of the heat transfer device 22 makes it possible to dimension the recuperator heat exchanger 16 such that it is particularly cost-effective or can be operated at a high flow rate, so that the purified synthesis gas may not yet have reached the desired second temperature T2 when fed S 17 to the second reactor 20.
  • the temperatures of the synthesis gas are shown as an example and as follows: The gasification S 10 or combustion S 10 takes place, for example, at around 920 ° C.
  • the synthesis gas produced in this way can therefore have a temperature of 900 ° C in step S 12, and it can cool down in the heat exchanger 16 by several fifty Kelvin, for example to 700 ° C, while giving off heat to the purified synthesis gas crossing in the heat exchanger 16.
  • the synthesis gas is then cooled to a cleaning temperature T3 of, for example, 300 ° C.
  • T3 a cleaning temperature of, for example, 300 ° C.
  • the cleaned synthesis gas can then be heated in the heat exchanger 16 by several fifty Kelvin, for example to 600 ° C.
  • an RWGS catalyst 20 is provided in the second reactor 20, in which the RWGS reaction takes place particularly favorably at high temperatures, for example above 700 ° C or above 750 ° C, the heat required for this can simply be provided by the exothermic and sufficiently warm first reaction process by means of the heat transfer device 22.
  • the synthesis gas can be purified thanks to the purification column 13+14 arranged upstream of the RWGS catalyst 20 in such a way that the service life of the RWGS catalyst 20 is further improved.
  • the heat loss required due to the purification can be compensated by means of the heat exchanger 16. In this way, the purification can take place without the need for additional external energy input to reheat the purified synthesis gas.
  • Figure 4 schematically shows a further embodiment of a plant for carrying out the process, wherein the plant 1 comprises two first reactors 10, the synthesis gas streams produced from which are combined in a Y-scheme before the methanol synthesis 50, in particular before the cooling stage 30.
  • the gasification reactor 10 and its associated RWGS catalyst 20 can be operated independently of the combustion reactor 10 and its associated RWGS catalyst 20 with regard to the reaction conditions of pressure and temperature. This allows a high degree of freedom in process control, while the downstream stages, i.e. the cleaning column 13 + 14 and the cooling stage 30, the compressor 40 and the synthesis loop 50 can be used jointly for the first two reactors 10.
  • one cleaning column 13 + 14 and one heat exchanger 16 can each be arranged upstream of a single RWGS reactor 20, as basically shown in Fig. 3b.
  • the advantages of the improved service life of the RWGS catalyst 20 can be combined with the advantages of the arrangement of two first reactors in the Y-scheme, namely that a greater variety of biomass reactants can be processed as needed by means of gasification or combustion, while saving on a second RWGS reactor.
  • recuperator heat exchanger 16 can be provided in all embodiments, in particular if the RWGS catalyst 20 is not arranged adjacent to the first reactor 10.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé et une installation de production de méthanol, comprenant : la réalisation (S10) d'un premier procédé de réaction à une première température (T1), le premier procédé de réaction, à l'aide de biomasse et d'oxygène, produisant un gaz de synthèse contenant du dioxyde de carbone (CO2); la mise en œuvre (S20) d'un second procédé de réaction sous la forme d'une réaction de conversion inverse eau-gaz à une seconde température (T2) à l'aide du gaz de synthèse produit, le second procédé de réaction augmentant un composant de monoxyde de carbone (CO) dans le gaz de synthèse, la seconde température (T2) étant supérieure à 400°C; la réalisation (S50) d'une synthèse de méthanol à l'aide du gaz de synthèse pour produire du méthanol. L'invention concerne en outre une installation conçue pour mettre en œuvre le procédé.
PCT/EP2024/074641 2023-11-13 2024-09-04 Procédé et installation de production de méthanol Pending WO2025103631A1 (fr)

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DE102023211272.8A DE102023211272A1 (de) 2023-11-13 2023-11-13 Verfahren und Anlage zum Herstellen von Methanol
DE102023211272.8 2023-11-13

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Publication number Priority date Publication date Assignee Title
WO2023110526A1 (fr) * 2021-12-14 2023-06-22 Casale Sa Production de méthanol à partir d'une gazéification de biomasse

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DE4328644A1 (de) * 1993-08-26 1995-04-13 Bfi Entsorgungstech Verfahren und Vorrichtung zur Erzeugung von Methanol
US6571747B1 (en) * 1999-03-26 2003-06-03 Michael Prestel Method and device for producing energy or methanol
DE102012112705A1 (de) * 2012-12-20 2014-06-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Herstellung von Methanol aus Kohlendioxid
DE102014016407A1 (de) * 2014-11-05 2016-05-12 Linde Aktiengesellschaft Verfahren zur Produktion von Synthesegas
WO2020048809A1 (fr) * 2018-09-04 2020-03-12 Basf Se Procédé de production de méthanol à partir de gaz de synthèse sans émission de dioxyde de carbone
EP4197994B1 (fr) * 2021-12-20 2024-09-11 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé et installation de production de méthanol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023110526A1 (fr) * 2021-12-14 2023-06-22 Casale Sa Production de méthanol à partir d'une gazéification de biomasse

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