WO2025008365A1 - Device and method for creating hydrogen and carbon dioxide product streams - Google Patents

Abstract

The invention relates to a method for creating hydrogen and carbon dioxide product streams, comprising: generating, by means of the thermochemical conversion of an organic feed substance in a gasification unit, an untreated product gas and a solid residue, wherein optionally a flue gas is additionally generated by combusting at least some of the solid residue; treating the untreated product gas to generate a treated product gas; subjecting the treated product gas to a catalyst-supported water-gas shift reaction to obtain a conditioned product gas; separating carbon dioxide from the conditioned product gas or from the flue gas to generate the carbon dioxide product stream; separating hydrogen from at least some of the conditioned product gas in a hydrogen separation system to generate the hydrogen product stream; returning a residual gas containing carbon monoxide and hydrogen from the hydrogen separation system to the gasification unit; and thermally recycling the returned residual gas in the gasification unit.

Description

APPARATUS AND METHOD FOR PRODUCING HYDROGEN AND CARBON DIOXIDE PRODUCT STREAMS

The present invention relates to a device and a method for producing a hydrogen product stream and a carbon dioxide product stream, in particular by at least partial thermochemical conversion of an organic feedstock.

The thermochemical conversion, in particular pyrolysis and/or gasification and/or oxidation, of at least part of a solid, liquid or gaseous organic starting material or feedstock using a gasifier with subsequent separation of the hydrogen from the gasifier effluent is a known technique for producing hydrogen.

It is an object of the invention to provide an improved method and apparatus for producing a hydrogen product stream and a carbon dioxide product stream.

This object is achieved according to the teaching of the independent claims. Various embodiments and developments of the invention are the subject of the subclaims.

A first aspect of the invention relates to a process for producing a hydrogen product stream and a carbon dioxide product stream, the process comprising:

Introducing an organic feedstock into a gasification unit, in particular into a gasifier of the gasification unit, and generating, by means of thermochemical conversion of the feedstock, an untreated product gas which contains carbon monoxide and hydrogen, and a solid residue, in some embodiments a pyrolysis coke, wherein optionally at least a part of the solid residue is introduced into a combustion unit, in particular contained in the gasification unit, and the solid residue is burned in the combustion unit to generate a flue gas containing carbon dioxide,

Treating the untreated product gas, in some embodiments by means of one or more treatment devices arranged downstream of the gasification unit, in particular the gasifier, to generate a treated product gas containing carbon monoxide and hydrogen,

introducing the treated product gas and water vapor into a water-gas shift reactor, and subjecting the treated product gas to a catalytically assisted water-gas shift reaction to obtain a conditioned product gas which has an increased hydrogen content compared to the treated product gas and contains carbon dioxide,

introducing the conditioned product gas and/or the flue gas into at least one carbon dioxide separation system and separating carbon dioxide from the conditioned product gas and/or the flue gas in the at least one carbon dioxide separation system to produce the carbon dioxide product stream,

introducing at least a portion of the conditioned product gas into a hydrogen separation system and separating hydrogen from the at least a portion of the conditioned product gas in the hydrogen separation system to produce the hydrogen product stream,

Returning a residual gas containing carbon monoxide and hydrogen from the hydrogen separation system to the gasification unit and thermally utilizing the returned residual gas in the gasification unit, in some embodiments in a combustion unit of the gasification unit.

In some embodiments, this makes it possible to thermally utilize the residual gas remaining after the hydrogen has been separated from the conditioned product gas in the gasification unit. The thermal utilization can involve burning the recycled residual gas, in some embodiments in the combustion unit of the gasification unit to generate the or at least part of the heat energy required for the thermochemical conversion. In some embodiments, this combustion unit of the gasification unit may be or include the firing unit. In some other embodiments, this combustion unit of the gasification unit may be different from the firing unit.

In some designs, the thermochemical conversion of the feedstock takes place in the carburetor.

In some embodiments, the untreated product gas is a hydrogen-containing, in particular hydrogen-rich, gas mixture, wherein the hydrogen content can be in the range of 10 vol.% to 30 vol.%, and the gas mixture can also contain carbon monoxide and other components.

In some embodiments, the untreated product gas contains carbon dioxide, wherein the conditioned product gas obtained by the water-gas shift reaction has an increased carbon dioxide content compared to the untreated product gas.

In some embodiments, a thermochemical conversion of the feedstock is understood to mean pyrolysis, gasification, a drying process, in particular torrefaction, or a combination of two or more of pyrolysis, gasification and the drying process.

In this case, the thermochemical conversion of the organic feedstock is effected, for example, by means of a gasification medium fed to the gasification unit, in particular the gasifier, which may contain, for example, air, oxygen, carbon dioxide or water vapor, and the supply of heat (energy).

The organic feedstock may, for example, contain biomass, in some embodiments sewage sludge, waste fractions, or generally plant or animal products such as excrement. Furthermore, the organic feedstock may contain one or more, for example from or using Waste, in some versions household waste and/or industrial waste and/or plastic waste, and substitute fuel.

In some embodiments, the gasification may include reforming a pyrolysis gas generated during pyrolysis of the organic feedstock using a reforming medium, for example steam or a fluid mixture with or without steam, for example carbon dioxide, to generate the untreated product gas. In this case, the gasification unit, in particular the gasifier, may include a pyrolysis reactor for pyrolyzing the organic feedstock and a reformer downstream of the pyrolysis reactor for reforming the pyrolysis gas.

In some embodiments, the generated flue gas can be used to heat ceramic balls, for example in a heat transfer medium preheater unit arranged above the reformer, whereby the heated ceramic balls as a heat transfer medium pass through the reformer and the pyrolysis reactor as a moving bed to provide heat energy for the respective gasification reactions.

Preferably, steam is used as the gasification medium, since this enables a reduction in the nitrogen content and an increase in the hydrogen content in the untreated product gas compared to the use of air as the gasification medium.

In addition, this can achieve a reduction in the volume of the untreated product gas and thus also a reduction in costs for all further process steps, since, as a result of the smaller volume, units or components of a device used to carry out the process according to the invention with smaller dimensions can be used for the further process steps.

Furthermore, the reduction of the nitrogen content in the untreated product gas enables or improves the use of pressure swing adsorption (PSA) described later to separate the hydrogen from the conditioned product gas and to generate the hydrogen product stream in the hydrogen separation system, since the separation of nitrogen and hydrogen using PSA is difficult due to the very similar adsorption properties of the two gases and thus sufficient purity of the hydrogen product stream produced would not be guaranteed.

The untreated product gas obtained by the thermochemical conversion may contain, for example, tar, ammonia, hydrogen sulphide and the like.

Part of the (thermal) energy required for the thermochemical conversion of the feedstock can, for example, be generated in the combustion unit by combustion of fuels supplied to the gasification unit, which in some designs are gaseous.

In some embodiments, the treatment of the untreated product gas comprises a post-reforming in a post-reforming unit, a cleaning in a cleaning unit and a compression in a compression unit, wherein during the post-reforming at least parts of tar components of the untreated product gas are removed, in some embodiments by oxidation of tar components, and thermal energy is released, wherein at least part of the released thermal energy is supplied to a water stream, for example using a heat exchanger, in order to generate water vapor, wherein the cleaning is downstream of the post-reforming, and during the cleaning at least chlorine and / or sulfur is removed from a product gas reformed by means of the post-reforming in order to obtain a purified product gas, wherein the compression is downstream of the cleaning, and during the compression the purified product gas is compressed in order to obtain the treated product gas.

In some embodiments, the post-reforming can be regarded as an improvement of a reforming process taking place in the gasification unit during the thermo-chemical conversion of the feedstock. In some embodiments, the post-reforming is carried out catalytically, i.e. using a suitable catalyst, in particular by Catalytic Partial Oxidation (CPOX).

In some embodiments, oxygen is added to the untreated product gas during post-reforming in order to partially oxidize the untreated product gas by means of an exothermic reaction, in some embodiments by thermal partial oxidation (TPOX), and to obtain the post-reformed product gas.

In this case, the temperatures of the gases in question, in some embodiments the temperature of the post-reformed product gas, and optionally the temperatures of solids entrained in the post-reformed product gas, can be in the range from 800 °C to 900 °C due to the course of the exothermic catalytic partial oxidation, and in the range from 1200 °C to 1400 °C due to the course of the (exothermic) thermal partial oxidation.

During the purification, for example, the chlorine and sulphur components and similar components, for example in the form of dust, which are contained in the post-reformed product gas can be removed from the post-reformed product gas by generally known purification processes in which, for example, one or more scrubber stages, which may include a Venturi scrubber stage, are used.

During compression, the purified product gas can, for example, be compressed in such a way that the compressed or treated product gas has an overpressure within a range of about 1.5 MPa to about 2.0 MPa. This makes it possible in particular that in a later process step or in the hydrogen separation system arranged downstream, the gas mixture present there, in some embodiments at least a portion of the conditioned product gas, has a pressure required for a hydrogen pressure swing adsorption described below and carried out by the hydrogen separation system to separate the hydrogen. In some embodiments, at least a portion of the carbon dioxide separated in the at least one carbon dioxide separation system is added to the post-reformed product gas prior to purification in a cooling unit to cause an endothermic Boudouard reaction of carbon dioxide of the at least a portion of the carbon dioxide separated in the at least one carbon dioxide separation system with carbon contained in the post-reformed product gas, and thus increase a carbon monoxide content in the post-reformed product gas and cool the post-reformed product gas, wherein the post-reformed cooled product gas is subsequently fed to the purification stage to purify the post-reformed cooled product gas to obtain the purified product gas.

zwischen dem in dem nachreformierten Produktgas enthaltenen Kohlenstoff und dem zumindest einen Teil des in dem zumindest einen Kohlenstoffdioxid- Trennsystem abgetrennten Kohlenstoffdioxids, welche in Richtung nach links endotherm verläuft, nach links zu verschieben, sodass der Kohlenstoffmonoxid- Gehalt in dem nachreformierten Produktgas erhöht wird und zugleich das nachreformierte Produktgas abgekühlt wird, um das nachreformierte abgekühlte Produktgas zu erhalten. In some embodiments, in which oxygen is added to the untreated product gas during the post-reforming process in order to partially oxidize the untreated product gas by means of the exothermic reaction and to obtain the post-reformed product gas, the fact that the post-reformed product gas has a sufficiently high temperature to reach the Boudouard equilibrium of the Boudouard reaction is used:

between the carbon contained in the post-reformed product gas and the at least part of the carbon dioxide separated in the at least one carbon dioxide separation system, which is endothermic in the direction to the left, so that the carbon monoxide content in the post-reformed product gas is increased and at the same time the post-reformed product gas is cooled in order to obtain the post-reformed cooled product gas.

In some embodiments, at least part of the water vapor generated in the gasification unit, in particular in the gasifier, is used as a gasification medium, in particular in the case where oxygen is added to the untreated product gas during the post-reforming in order to convert the untreated product gas into oxygen by means of the exothermic reaction, in some embodiments by Thermal Partial Oxidation (TPOX) to partially oxidize and obtain the reformed product gas.

In some embodiments, at least part of the steam generated is used to generate electricity in a combined heat and power plant, in particular by means of a steam turbine.

In some embodiments, a first carbon dioxide separation system of the at least one carbon dioxide separation system is designed as a carbon dioxide pressure swing adsorption unit, wherein the separation of carbon dioxide from the conditioned product gas is carried out by a pressure swing adsorption process.

A first carbon dioxide separation system of the at least one carbon dioxide separation system is preferably designed as a carbon dioxide pressure swing adsorption unit in embodiments in which the conditioned product gas has a low nitrogen content due to the use of water vapor as a gasification medium in the gasification unit or contains no nitrogen, wherein the conditioned product gas has a low carbon monoxide content suitable for carbon dioxide pressure swing adsorption due to the water gas shift reaction carried out in the water gas shift reactor. This requirement (low carbon monoxide content) enables the possibility of using carbon dioxide pressure swing adsorption to separate the carbon dioxide in some embodiments.

Furthermore, in order to carry out the carbon dioxide pressure swing adsorption, it is necessary that the conditioned product gas has a minimum pressure, so that in the case of using the carbon dioxide pressure swing adsorption unit for separating the carbon dioxide, the compression of the purified product gas preferably also takes place in the compression unit, so that the conditioned product gas continues to have the high pressure required for the pressure swing absorption of carbon dioxide. In some designs, the hydrogen separation system is designed as a hydrogen pressure swing adsorption unit, whereby the hydrogen is separated by a pressure swing adsorption process.

The hydrogen separation system is preferably designed as a hydrogen pressure swing adsorption unit in which the conditioned product gas has a low nitrogen content or contains no nitrogen due to the use of water vapor as a gasification medium in the gasification unit.

It is also advantageous for the separation of hydrogen by the pressure swing adsorption process if at least part of the conditioned product gas has a minimum pressure. Therefore, the separation of hydrogen by the pressure swing adsorption process is preferably carried out in embodiments in which the purified product gas is compressed in the compression unit.

Since the purified product gas should be compressed in the compression unit for separating the hydrogen by the pressure swing adsorption process from at least a portion of the conditioned product gas, in some embodiments it must be compressed, the carbon dioxide can advantageously be separated from the conditioned product gas by the pressure swing adsorption process without any significant additional compression effort being required for the carbon dioxide separation.

In some embodiments, at least a portion of the carbon dioxide separated in the first carbon dioxide separation system is returned to the gasification unit, in particular to the gasifier, and used in the gasification unit, in particular in the gasifier, as a supplementary gasification medium.

As a result, in some designs, less or no water vapor is required as a gasification medium in the gasification unit, in particular in the gasifier, so that the excess water vapor can be used for other purposes, for example, as already described above, to generate electricity in the cogeneration plant. In some embodiments, at least a portion of the carbon dioxide separated in the first carbon dioxide separation system is used to gasify the solid residue in a gasifier to produce a product gas stream, wherein the product gas stream is added to the post-reformed product gas, in some embodiments prior to the purification step.

As a result, in some embodiments, an amount of the carbon dioxide product stream produced and/or an amount of the hydrogen product stream produced, i.e. a carbon dioxide yield and/or a hydrogen yield when carrying out the process according to the invention, can be increased.

In some embodiments, at least a portion of the carbon dioxide separated in the first carbon dioxide separation system is used to physically activate the solid residue in a gasification device to obtain an activated solid residue, in particular an activated pyrolysis coke.

The activated solid residue can then be used as a product for industrial applications, for example in the iron or steel industry, in some versions as activated carbon for activated carbon filters.

In some embodiments, the separation of carbon dioxide from the flue gas is carried out by carrying out an amine scrubbing process in a second carbon dioxide separation system of the at least one carbon dioxide separation system designed as an amine scrubbing unit.

A second aspect of the invention relates to a device which is adapted to carry out at least one embodiment of the method described above.

In some embodiments, the device comprises: a gasification unit which is designed to receive an organic feedstock, wherein in particular a gasifier of the gasification unit is designed to receive the organic feedstock and by means of thermal chemical conversion of the feedstock to generate an untreated product gas which contains carbon monoxide and hydrogen, and a solid residue, in some embodiments a pyrolysis coke, wherein the device, in some embodiments the gasification unit, optionally further comprises a firing unit which is configured to burn at least a portion of the solid residue to generate a flue gas which contains carbon dioxide, one or more treatment devices which are configured to treat the untreated product gas to generate a treated product gas which contains carbon monoxide and hydrogen, a water-gas shift reactor which is configured to receive the treated product gas and water vapor, and to subject the treated product gas to a catalytically assisted water-gas shift reaction to obtain a conditioned product gas which has an increased hydrogen content compared to the treated product gas and contains carbon dioxide, at least one carbon dioxide separation system which is configured to process the conditioned product gas and/or to receive the flue gas and to separate carbon dioxide from the conditioned product gas and/or the flue gas to produce the carbon dioxide product stream, a hydrogen separation system which is designed to receive at least a portion of the conditioned product gas and to separate hydrogen from the at least a portion of the conditioned product gas to produce the hydrogen product stream, and a line arrangement which is designed to return a residual gas containing carbon monoxide and hydrogen from the hydrogen separation system to the gasification unit, wherein the gasification unit, in some embodiments a combustion unit of the gasification unit, is designed to thermally utilize the recycled residual gas.

The thermal utilization may include burning the recycled residual gas, in some embodiments in the combustion unit of the gasification unit, to generate the or at least part of the thermal energy required for the thermochemical conversion. In some embodiments, this combustion unit of the gasification unit may be or include the firing unit. In some other embodiments, this combustion unit of the gasification unit may be different from the firing unit.

In some embodiments, the untreated product gas contains carbon dioxide, wherein the conditioned product gas obtained by the water-gas shift reaction has an increased carbon dioxide content compared to the untreated product gas.

The features and advantages described with respect to the first aspect of the invention and its advantageous embodiment also apply, at least where technically reasonable, to the second aspect of the invention and its advantageous embodiment and vice versa.

Further advantages, features and possible applications of the present invention will become apparent from the following description in conjunction with the figures, in which the same reference numerals are used throughout for the same or corresponding elements of the invention. They show, at least partially schematically:

Fig. 1 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment,

Fig. 2 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment, Fig. 3 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment,

Fig. 4 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment,

Fig. 5 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment,

Fig. 6 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment,

Fig. 7 shows an apparatus for producing a hydrogen product stream and a carbon dioxide product stream according to an embodiment, and

Fig. 8 is a flow chart illustrating the process according to the invention for producing a hydrogen product stream and a carbon dioxide product stream.

Fig. 1 shows a device for generating a hydrogen product stream and a carbon dioxide product stream according to one embodiment. The device is particularly designed to carry out at least one embodiment of the method according to the invention.

The device 1001 has a gasification unit 10, 11 which is designed to receive an organic feedstock 1, which may contain biomass, for example, wherein in particular a gasifier 10 of the gasification unit 10, 11 is designed to receive the organic feedstock 1 and to generate an untreated product gas P1, which contains carbon monoxide and hydrogen, and a solid residue P14, in some embodiments a pyrolysis coke, by means of thermochemical conversion of the feedstock 1 or at least a part thereof.

The thermochemical conversion of the feedstock 1 is understood in some embodiments to mean pyrolysis, gasification, a drying process, in particular torrefaction, or a combination of two or more of the pyrolysis, gasification and drying processes.

In this case, the thermochemical conversion is brought about, for example, by means of a gasification medium supplied via lines not shown, in particular the gasifier 10, which may contain, for example, air, oxygen, carbon dioxide or water vapor, and the supply of heat (energy).

The organic feedstock 1 can contain, for example, biomass, in some embodiments sewage sludge, waste fractions, or generally plant or animal products such as excrement. Furthermore, the organic feedstock 1 can contain one or more substitute fuels produced, for example, from or using garbage, in some embodiments household waste and/or industrial waste and/or plastic waste.

In some embodiments, the gasification may include reforming a pyrolysis gas generated during pyrolysis of the feedstock 1 using a reforming medium, for example steam or a fluid mixture with or without steam, for example carbon dioxide, in order to generate the untreated product gas P1. In this case, the gasification unit 10, 11, in particular the gasifier 10, may include a pyrolysis reactor and a reformer downstream of the pyrolysis reactor, which are not shown separately in the figures.

The device 1001, in some embodiments the gasification unit 10, 11, further comprises a combustion unit which is configured to generate at least a portion of the thermal energy required for the thermochemical conversion. In some embodiments, the combustion unit is a firing unit 11 which is further configured to burn at least a portion of the solid residue P14 to generate a flue gas P21 which contains carbon dioxide. In some other embodiments, this combustion unit of the gasification unit 10, 11 may be different from the firing unit 11. In some embodiments, the generated flue gas can be used to heat ceramic balls, for example in a heat transfer medium preheater unit arranged above the reformer (not shown in the figures), wherein the heated ceramic balls as a heat transfer medium pass through the reformer and the pyrolysis reactor as a moving bed to provide heat energy for the respective gasification reactions.

Preferably, steam is used as the gasification medium, since this enables a reduction in the nitrogen content and an increase in the hydrogen content in the untreated product gas P1 to be achieved compared to the use of air as the gasification medium.

In addition, this can achieve a reduction in the volume of the untreated product gas P1 and thus also a cost reduction for the device 1001 or all further process steps, since due to the smaller volume, units or components of the device with smaller dimensions can be used for the further process steps.

Furthermore, the reduction of the nitrogen content in the untreated product gas P1 enables or improves the use of a pressure swing adsorption (PSA) described later for separating hydrogen from the (conditioned) product gas P5 in a hydrogen separation system 70 described below, since a separation of nitrogen and hydrogen by means of PSA is difficult due to the very similar adsorption properties of the two gases and thus sufficient purity of the hydrogen product stream P10 to be produced would not be guaranteed.

The untreated product gas P1 obtained by the thermochemical conversion may contain, for example, tar, ammonia, hydrogen sulphide and the like.

Downstream of the gasification unit 10, 11, in particular the gasifier 10 of the gasification unit 10, 11, treatment devices 20, 30, 40, in particular a post-reforming unit 20, a cleaning unit 30 and a compression unit 40 are arranged one after the other, which are designed to to treat the untreated product gas P1 or a respective incompletely treated product gas present after a respective one of the treatment devices 20, 30 whose properties have changed in order to obtain or generate a treated product gas P4 which contains carbon monoxide and hydrogen.

Here, the gasification unit 10, 11, in particular the gasifier 10, is connected via lines not shown to the post-reforming unit 20, which is designed to receive the untreated product gas P1 from the gasification unit 10, 11 and to subject the untreated product gas P1 to a post-reforming, in which at least parts of tar components contained in the untreated product gas P1 are removed from the untreated product gas P1, in particular by a (partial) oxidation of the tar components, in order to obtain a post-reformed product gas P2.

The post-reforming can be carried out catalytically, i.e. using a suitable catalyst, in particular by catalytic partial oxidation (CPOX), or by thermal partial oxidation (TPOX), whereby the temperatures of the gases and optionally solids in question can be in the range from 800 °C to 900 °C due to the catalytic partial oxidation process, and in the range from 1200 °C to 1400 °C due to the thermal partial oxidation process.

The thermal energy released during the subsequent reforming is, at least in part, fed to a water stream, for example by means of a heat exchanger, in particular in the case where the subsequent reforming is carried out by thermal partial oxidation, in order to evaporate the water and thereby generate water vapor P7, P8. In this case, at least a portion P7 of the generated water vapor P7, P8 is passed via lines (not shown) into the gasification unit 10, 11, in particular the gasifier 10, and used there as an (additional) gasification medium.

The post-reforming unit 20 is connected via lines not shown to the cleaning unit 30, which is designed to receive the post-reformed product gas P2 from the post-reforming unit 20 and to reformed product gas P2 is subjected to a purification in order to obtain a purified product gas P3.

During the purification, for example, chlorine and sulphur components as well as similar components, for example in the form of dust, which are contained in the post-reformed product gas P2 can be removed from the post-reformed product gas P2 by generally known purification processes in which, for example, one or more scrubber stages, which may include a Venturi scrubber stage, are used.

The cleaning unit 30 is connected via lines not shown to the compression unit 40, which is configured to receive the cleaned product gas P3 from the cleaning unit 30 and to compress the cleaned product gas P3 in order to generate or obtain a compressed or treated product gas P4 which contains carbon monoxide and hydrogen.

In this case, the compression unit 40 can be set up, for example, to compress the purified product gas P3 in such a way that the compressed or treated product gas P4 has an (over)pressure within a range of approximately 1.5 MPa to approximately 2.0 MPa. This makes it possible in particular that in a later process step or in a downstream hydrogen separation system 70 of the device 1001, the gas mixture present there has a pressure required for hydrogen pressure swing adsorption to separate hydrogen.

The compression unit 40 is connected via lines not shown to a water-gas shift reactor 50 which is designed to receive the treated product gas P4 from the compression unit 40. Furthermore, the water-gas shift reactor 50 is designed to receive at least a portion P8 of the water vapor P7, P8 generated using the thermal energy generated in the post-reforming unit 20 and to subject the treated product gas P4 (using the portion P8 of the water vapor and a suitable catalyst) to a catalytically assisted water-gas shift reaction (WGS) which is characterized by the following reaction equation: co + H ₂ O CO ₂ + H ₂ , in which the chemical equilibrium is shifted to the right to obtain a conditioned product gas P5 having an increased hydrogen and carbon dioxide content compared to the treated product gas P4.

The water-gas shift reactor 50 is connected via lines (not shown) to a carbon dioxide separation system 60, which is designed to receive the conditioned product gas P5 from the water-gas shift reactor 50 and to separate carbon dioxide from the conditioned product gas P5 in order to produce a carbon dioxide product stream P11. The carbon dioxide product stream P11 can then be post-processed in one or more post-processing devices (not shown), for example a cleaning device, a drying device or a compression device, and then filled into appropriate containers and used for various applications.

Here, since the purified product gas P3 was compressed in the compression unit 40 and the conditioned product gas P5 still has a high pressure required for pressure swing absorption of carbon dioxide, the carbon dioxide separation system 60 can be designed, for example, as a carbon dioxide pressure swing adsorption unit, and the separation of carbon dioxide from the conditioned product gas P5 can be carried out by a pressure swing adsorption process for separating carbon dioxide, in particular using the carbon dioxide pressure swing adsorption unit.

The carbon dioxide separation system 60 is connected via lines not shown to a hydrogen separation system 70, which is designed to receive at least a portion P6 of the conditioned product gas P5, in particular a carbon dioxide-poor residual gas from the conditioned product gas P5 introduced into the carbon dioxide separation system 60, from the carbon dioxide separation system 60, and to separate hydrogen from the at least a portion P6 of the conditioned product gas P5 in order to to generate product stream P10. The hydrogen product stream P10 can then be filled into appropriate containers and used for various applications.

In this case, the hydrogen separation system 70 can be designed, for example, as a hydrogen pressure swing adsorption unit, and the separation of hydrogen from the conditioned product gas can be carried out by a pressure swing adsorption process for separating hydrogen.

Pressure swing adsorption processes and correspondingly designed pressure swing adsorption units are generally known, so that a more detailed description of the carbon dioxide pressure swing adsorption unit and the hydrogen pressure swing adsorption unit or the implementation of the corresponding processes can be omitted here.

The hydrogen separation system 70 is connected via lines not shown to the gasification unit 10, 11, in particular the combustion unit, which is designed to receive a residual gas P13 containing carbon monoxide and hydrogen, which remains after the separation of the hydrogen from the part P6 of the conditioned product gas P5, from the hydrogen separation system 70, in particular by recirculation.

In the embodiment shown in Fig. 1, the combustion unit of the gasification unit 10, 11 is different from the firing unit 11 and is not shown separately.

In an embodiment not shown, the combustion unit of the gasification unit 10, 11 can be or contain the firing unit 11. In this case, in contrast to the illustration in Fig. 1, the end of the arrow emanating from the hydrogen separation system 70 to illustrate the flow of the residual gas P13 would be connected to the firing unit 11 or point to it.

The gasification unit 10, 11, in particular the combustion unit, is designed to process the (recirculated) residual gas P13, in particular the to thermally utilize, in particular to burn, the high-calorific components hydrogen and carbon monoxide in order to generate at least part of the heat (energy) required for the thermochemical conversion.

Fig. 2 shows a device for generating a hydrogen product stream and a carbon dioxide product stream according to one embodiment. The device is particularly designed to carry out at least one embodiment of the method according to the invention.

The device 1002 shown in Fig. 2 corresponds in large parts to the device 1001 shown in Fig. 1. In order to avoid repetition, only the differences between the device 1002 shown in Fig. 2 and the device 1001 shown in Fig. 1 are discussed below.

In the embodiment shown in Fig. 2, at least a portion P1 T" of the carbon dioxide product stream P11 generated by separating carbon dioxide from the conditioned product gas P5 is returned to the gasification unit 10, 11, in particular to the gasifier 10, which is or can be used in the gasification unit 10, 11, in particular the gasifier 10, as a supplementary gasification medium. As a result, less, or in some embodiments no, water vapor is required for the thermochemical conversion of the feedstock 1, whereby a portion P7 of the generated water vapor that is returned to the gasification unit 10, 11, in particular to the gasifier 10, can at least be reduced, so that a portion P9 of the generated water vapor P7, P8, P9 can be used elsewhere, preferably for generating electricity P12 in a cogeneration plant 80 connected to the post-reforming unit 20 via lines not shown, in particular by means of a steam turbine.

The device 1003 shown in Fig. 3 corresponds in large parts to the device 1001 shown in Fig. 1. In order to avoid repetition, only the differences between the device 1003 shown in Fig. 3 and the device 1001 shown in Fig. 1 are discussed below. In the embodiment shown in Fig. 3, the gasification unit 10, 11, in particular the firing unit 11, is connected via lines not shown to a carbon dioxide separation system 90, which is designed to receive the flue gas P21 produced by the combustion of the solid residue P14 from the gasification unit 10, 11, in particular the firing unit 11, and to separate carbon dioxide from the flue gas P21, for example by amine scrubbing or cryogenic carbon dioxide separation, in order to produce the carbon dioxide product stream P23 and a carbon dioxide-poor flue gas P22.

In this case, the carbon dioxide separation system 60 shown in Fig. 1 can be omitted, so that the conditioned product gas P5 from the water-gas shift reactor 50 can be passed directly into the hydrogen separation system 70, whereby in particular the carbon dioxide content in the residual gas P13 can be increased.

The device 1004 shown in Fig. 4 corresponds in large parts to the device 1003 shown in Fig. 3. In order to avoid repetition, only the differences between the device 1004 shown in Fig. 4 and the device 1003 shown in Fig. 3 are discussed below.

In the embodiment shown in Fig. 4, a portion P3' of the product gas P3 cleaned in the cleaning unit 30 is fed to a steam generator 100 via pipes (not shown) and used therein to generate water vapor P25, for example by burning the portion P3' of the cleaned product gas P3 to generate thermal energy, and at least a portion of the thermal energy generated is used to heat water, for example using a heat exchanger. The steam generator 100 is connected via lines (not shown) to the carbon dioxide separation system 90, which is designed as an amine scrubbing unit and is set up to separate the carbon dioxide from the flue gas P21 by carrying out an amine scrubbing process in which the carbon dioxide is removed or stripped from the corresponding scrubbing medium using the steam supplied by the steam generator 100. As a result, a specific hydrogen yield of the device 1004 decreases in comparison to the specific hydrogen yield of the devices 1001, 1002, 1003 shown in Figs. 1 to 3, since a portion P3' of the purified product gas P3 is diverted to generate steam, but the carbon footprint of the (produced) hydrogen also decreases, since a larger amount of carbon dioxide can be separated from the flue gas P21 than from the conditioned product gas P5.

The device 1005 shown in Fig. 5 corresponds in large parts to the device 1001 shown in Fig. 1. In order to avoid repetition, only the differences between the device 1005 shown in Fig. 5 and the device 1001 shown in Fig. 1 are discussed below.

In the embodiment shown in Fig. 5, the post-reforming in the post-reforming unit 20 is carried out by adding oxygen (not shown in Fig. 5) to the untreated product gas P1 in order to form a substoichiometric fuel-oxygen mixture of the carbon monoxide and hydrogen contained in the untreated product gas P1 and the added oxygen in order to partially oxidize or burn the untreated product gas P1 by means of an exothermic reaction, which is also referred to as thermal partial oxidation (TPOX), and thus to obtain a post-reformed product gas P2 with a temperature in the range of approximately 1200 °C to 1400 °C.

In the embodiment shown in Fig. 5, in contrast to the embodiment shown in Fig. 1, the post-reformed product gas P2 is not fed directly into the cleaning unit 30, but is first fed into the cooling unit 110 via a line (not shown) which connects the post-reforming unit 20 to a cooling unit 110.

At the same time, at least a portion P1 T of the carbon dioxide separated in the carbon dioxide separation system 60 is branched off from the carbon dioxide separation system 60 and fed into the cooling unit 110. Due to the hot post-reformed product gas P2, the Boudouard equilibrium of the Boudouard reaction is: 2 CO C + CO ₂ between the carbon contained in the post-reformed product gas P2 and the at least a portion P1 T of the carbon dioxide separated in the carbon dioxide separation system 60, which is endothermic in the direction to the left, is shifted to the left, so that the carbon monoxide content in the post-reformed product gas P2 is increased and at the same time the post-reformed product gas P2 is cooled to obtain a post-reformed cooled product gas P2'.

The post-reformed cooled product gas P2' is then subjected to cleaning in the cleaning unit 30 and the cleaned product gas P3 is compressed in the compression unit 40 in order to obtain the compressed or treated product gas P4, which due to the Boudouard reaction taking place in the cooling unit 110 in the direction of the left-hand side of the equation has a high carbon monoxide content, or an increased carbon monoxide content compared to the embodiment shown in Fig. 1. This also makes it possible to increase the hydrogen yield, i.e. the hydrogen content of the conditioned product gas P5, in the water-gas shift reaction that subsequently takes place in the water-gas shift reactor 50.

The device 1006 shown in Fig. 6 corresponds in large parts to the device 1001 shown in Fig. 1. In order to avoid repetition, only the differences between the device 1006 shown in Fig. 6 and the device 1001 shown in Fig. 1 are discussed below.

In the embodiment shown in Fig. 6, the carbon dioxide separation system 60 is connected via lines not shown to a gasification device 120, which is connected to the gasifier 10 via lines not shown or a conveyor device not shown.

In this case, at least a portion P11" of the carbon dioxide separated in the carbon dioxide separation system 60 is used for gasification of the solid residue P14 produced during the thermochemical conversion of the feedstock 1, in particular pyrolysis coke, which is fed from the gasifier 10 into the gasification Device 120 or, for example, transported by means of the conveyor device, is used in the gasification device 120 to generate a product gas stream P15. This product gas stream P15 is then added to the post-reformed product gas P2, in particular before the cleaning unit 30.

This can increase the carbon dioxide yield and the hydrogen yield.

The device 1007 shown in Fig. 7 corresponds in large parts to the device 1001 shown in Fig. 1. In order to avoid repetition, only the differences between the device 1007 shown in Fig. 7 and the device 1001 shown in Fig. 1 are discussed below.

In the embodiment shown in Fig. 7, the carbon dioxide separation system 60 is connected via lines not shown to a gasification device 130, which may be similar or identical to the gasification device 120 shown in Fig. 6, and which is connected to the gasifier 10 via lines not shown or a conveyor device not shown.

In this case, at least a portion pn ¹ ” ¹ of the carbon dioxide separated in the carbon dioxide separation system 60 is used for the physical activation of a solid residue P14 produced during the thermochemical conversion of the feedstock 1, in particular due to incomplete gasification of the feedstock 1 in the gasifier 10, which is brought from the gasifier 10 into the gasification device 130 or transported, for example by means of the conveyor device, in the gasification device 130 in order to obtain an activated solid residue P16.

This activated solid residue P16 can then be used as a product for industrial applications, for example in the iron or steel industry, in particular as activated carbon for, for example, activated carbon filters.

Fig. 8 shows a flow chart to illustrate embodiments of the method according to the invention for producing a hydrogen product stream and a carbon dioxide product stream, which can be carried out in particular using one of the devices 1001, 1007 described above.

In a step S1, an organic feedstock 1 is introduced into a gasification unit 10, 11, in particular into a gasifier 10 of the gasification unit 10, 11, and an untreated product gas P1, which contains carbon monoxide and hydrogen, and a solid residue P14 are generated by means of thermochemical conversion of the feedstock 1, wherein optionally at least a portion of the solid residue P14 is introduced into a combustion unit 11, in particular contained in the gasification unit 10, 11, and the solid residue P14 is burned in the combustion unit 11 to generate a flue gas P21 which contains carbon dioxide.

In a step S2, the untreated product gas P1 is treated to generate a treated product gas P4 which contains carbon monoxide and hydrogen.

In a step S3, the treated product gas P4 and water vapor P8 are introduced into a water-gas shift reactor 50, and the treated product gas P4 is subjected to a catalytically assisted water-gas shift reaction in order to obtain a conditioned product gas P5 which has an increased hydrogen content compared to the treated product gas P4 and contains carbon dioxide.

In a step S4, the conditioned product gas P5 and/or the flue gas P21 are introduced into at least one carbon dioxide separation system 60, 90 and carbon dioxide is separated from the conditioned product gas P5 and/or the flue gas P21 in the at least one carbon dioxide separation system 60, 90 in order to generate the carbon dioxide product stream P11, P23.

In a step S5, at least a portion P5, P6 of the conditioned product gas P5 is introduced into a hydrogen separation system 70, and hydrogen is separated from the at least a portion P5, P6 of the conditioned product gas P5. product gas P5 in the hydrogen separation system 70 to produce the hydrogen product stream P10.

In a step S6, a residual gas P13 containing carbon monoxide and hydrogen is returned from the hydrogen separation system 70 to the gasification unit 10.

In a step S7, the recycled residual gas P13 is thermally utilized in the gasification unit 10, 11, in particular in a combustion unit of the gasification unit 10, 11.

In some embodiments, the treatment of the untreated product gas P1 can comprise post-reforming in a post-reforming unit 20, cleaning in a cleaning unit 30 and compression in a compression unit 40, wherein during the post-reforming at least parts of tar components of the untreated product gas P1 are removed, in particular by oxidation of tar components, and thermal energy is released, wherein at least part of the released thermal energy is fed to a water stream in order to generate water vapor P7, P8, P9, wherein the cleaning is downstream of the post-reforming, and during the cleaning at least chlorine and/or sulfur is removed from a product gas P2 reformed by means of the post-reforming in order to obtain a purified product gas P3, wherein the compression is downstream of the cleaning, and during the compression the purified product gas P3 is compressed in order to obtain the treated product gas P4.

In some designs, the post-reforming can be carried out catalytically.

In some embodiments, oxygen can be added to the untreated product gas P1 during the post-reforming step in order to partially oxidize the untreated product gas P1 by means of an exothermic reaction and to obtain the post-reformed product gas P2.

In some embodiments, at least a portion P1 T of the carbon dioxide separated in the at least one carbon dioxide separation system may be supplied to the post-reformed product gas P2 prior to purification in a cooling unit 110 in order to induce an endothermic Boudouard reaction of carbon dioxide of the at least a portion P1 T of the carbon dioxide separated in the at least one carbon dioxide separation system with carbon contained in the post-reformed product gas P2, and thus to increase a carbon monoxide content in the post-reformed product gas P2 and to cool the post-reformed product gas P2, wherein the post-reformed cooled product gas P2' is subsequently fed to the purification stage 30 in order to purify the post-reformed cooled product gas P2' to obtain the purified product gas P3.

In some embodiments, at least a portion P7 of the generated water vapor P7, P8, P9 can be used as a gasification medium in the gasification unit 10, 11, in particular in the gasifier 10.

In some embodiments, at least a portion P9 of the generated steam P7, P8, P9 can be used to generate electricity P12 in a combined heat and power plant 80, in particular by means of a steam turbine.

In some embodiments, a first carbon dioxide separation system 60 of the at least one carbon dioxide separation system 60, 90 may be designed as a carbon dioxide pressure swing adsorption unit, wherein the separation of carbon dioxide from the conditioned product gas may be carried out by a pressure swing adsorption process.

In some embodiments, the hydrogen separation system 70 may be designed as a hydrogen pressure swing adsorption unit, wherein the separation of the hydrogen may be carried out by a pressure swing adsorption process.

In some embodiments, at least a portion P1 T" of the carbon dioxide separated in the first carbon dioxide separation system 60 can be returned to the gasification unit 10, 11, in particular to the gasifier 10, and used in the gasification unit 10, 11, in particular in the gasifier 10, as a supplementary gasification medium. In some embodiments, at least a portion P1 T" of the carbon dioxide separated in the first carbon dioxide separation system 60 may be used to gasify the solid residue P14 in a gasification device 120 to produce a product gas stream P15, wherein the product gas stream P15 may be added to the post-reformed product gas P2 prior to the purification stage 30.

In some embodiments, at least a portion P11 of the carbon dioxide separated in the first carbon dioxide separation system 60 may be used to physically activate the solid residue P14 in a gasification device 120 to obtain an activated solid residue P16.

In some embodiments, the separation of carbon dioxide from the flue gas P21 can be carried out by carrying out an amine scrubbing process in a second carbon dioxide separation system 90 of the at least one carbon dioxide separation system 60, 90, designed as an amine scrubbing unit.

While at least one exemplary embodiment has been described above, it should be noted that a wide variety of variations exist. It should also be noted that the exemplary embodiments described are merely non-limiting examples and are not intended to limit the scope, applicability, or configuration of the devices and methods described herein. Rather, the foregoing description will provide a guide to those skilled in the art for implementing at least one exemplary embodiment, it being understood that various changes in the operation and arrangement of the elements described in an exemplary embodiment may be made without departing from the subject matter set forth in the appended claims and their legal equivalents.

Claims

PATENT CLAIMS 1. A process for producing a hydrogen product stream (P10) and a carbon dioxide product stream (P11, P23), the process comprising: Introducing an organic feedstock (1) into a gasification unit (10, 11), in particular into a gasifier (10) of the gasification unit (10, 11), and generating, by means of thermochemical conversion of the feedstock (1), an untreated product gas (P1) which contains carbon monoxide and hydrogen, and a solid residue (P14), in particular a pyrolysis coke, wherein optionally at least a portion of the solid residue (P14) is introduced into a firing unit (11), in particular contained in the gasification unit (10, 11), and the solid residue (P14) is burned in the firing unit (11) in order to generate a flue gas (P21) which contains carbon dioxide, Treating the untreated product gas (P1) to generate a treated product gas (P4) containing carbon monoxide and hydrogen, Introducing the treated product gas (P4) and water vapor (P8) into a water-gas shift reactor (50), and subjecting the treated product gas (P4) to a catalytically assisted water-gas shift reaction to obtain a conditioned product gas (P5) which has an increased hydrogen content compared to the treated product gas (P4) and contains carbon dioxide, Introducing the conditioned product gas (P5) and/or the flue gas (P21) into at least one carbon dioxide separation system (60, 90) and separating carbon dioxide from the conditioned product gas (P5) and/or the flue gas (P21) in the at least one carbon dioxide separation system (60, 90) to produce the carbon dioxide product stream (P11, P23), Introducing at least a portion (P5, P6) of the conditioned product gas (P5) into a hydrogen separation system (70) and separating hydrogen from the at least a portion (P5, P6) of the conditioned product gas (P5) in the hydrogen separation system (70) to produce the hydrogen product stream (P10), Returning a residual gas (P13) containing carbon monoxide and hydrogen from the hydrogen separation system (70) to the gasification unit (10, 11) and thermally utilizing the returned residual gas (P13) in the gasification unit (10, 11), in particular in a combustion unit of the gasification unit (10, 11). 2. Method according to claim 1, wherein the treatment of the untreated product gas (P1) comprises a post-reforming in a post-reforming unit (20), a cleaning in a cleaning unit (30) and a compression in a compression unit (40), wherein during the post-reforming at least parts of tar components of the untreated product gas (P1) are removed, in particular by oxidation of tar components, and thermal energy is released, wherein at least part of the released thermal energy is fed to a water stream in order to generate water vapor (P7, P8, P9), wherein the cleaning is downstream of the post-reforming, and during the cleaning at least chlorine and/or sulfur is removed from a product gas (P2) reformed by means of the post-reforming in order to obtain a purified product gas (P3), wherein the compression is downstream of the cleaning, and during the compression the purified product gas (P3) is compressed in order to obtain the treated product gas (P4). receive. 3. The process according to claim 2, wherein the reforming is carried out catalytically. 4. The process according to claim 2, wherein during the post-reforming, oxygen is added to the untreated product gas (P1) in order to To partially oxidize the product gas (P1) by means of an exothermic reaction and to obtain the reformed product gas (P2). 5. The method according to claim 4, wherein at least a portion (P1 T) of the carbon dioxide separated in the at least one carbon dioxide separation system (60) is added to the post-reformed product gas (P2) before purification in a cooling unit (110) in order to cause an endothermic Boudouard reaction of carbon dioxide of the at least a portion (P1 T) of the carbon dioxide separated in the at least one carbon dioxide separation system (60) with carbon contained in the post-reformed product gas (P2), and thus to increase a carbon monoxide content in the post-reformed product gas (P2) and to cool the post-reformed product gas (P2), wherein the post-reformed cooled product gas (P2') is subsequently fed to the purification stage (30) in order to purify the post-reformed cooled product gas (P2') in order to obtain the purified product gas (P3). 6. Method according to one of claims 2 to 5, wherein at least a part (P7) of the generated water vapor (P7, P8, P9) is used as a gasification medium in the gasification unit (10, 11), in particular in the gasifier (10). 7. Method according to one of claims 2 to 6, wherein at least a part (P9) of the generated water vapor (P7, P8, P9) is used to generate electricity (P12) in a combined heat and power plant (80), in particular by means of a steam turbine. 8. Method according to one of the preceding claims, in which a first carbon dioxide separation system (60) of the at least one carbon dioxide separation system (60, 90) is designed as a carbon dioxide pressure swing adsorption unit, and the separation of carbon dioxide from the conditioned product gas takes place by a pressure swing adsorption process. 9. Method according to one of the preceding claims, in which the hydrogen separation system (70) is designed as a hydrogen pressure swing adsorption unit, and the separation of the hydrogen is carried out by a pressure swing adsorption process. 10. Method according to one of the preceding claims, wherein at least a portion (P1 T") of the carbon dioxide separated in the first carbon dioxide separation system (60) is returned to the gasification unit (10, 11), in particular to the gasifier (10), and is used in the gasification unit (10, 11), in particular in the gasifier (10), as a supplementary gasification medium. 11. A process according to any one of the preceding claims, wherein at least a portion (P1 T") of the carbon dioxide separated in the first carbon dioxide separation system (60) is used to gasify the solid residue (P14) in a gasification device (120) to produce a product gas stream (P15), and the product gas stream (P15) is added to the post-reformed product gas (P2) before the purification stage (30). 12. The method according to any one of claims 1 to 10, wherein at least a portion (P11"'') of the carbon dioxide separated in the first carbon dioxide separation system (60) is used for physically activating the solid residue (P14) in a gasification device (130) to obtain an activated solid residue (P16). 13. Method according to one of the preceding claims, wherein the separation of carbon dioxide from the flue gas (P21) is carried out by carrying out an amine scrubbing process in a second carbon dioxide separation system (90) of the at least one carbon dioxide separation system (60, 90) designed as an amine scrubbing unit. 14. Device (1001, ..., 1007) which is arranged to carry out a method according to one of claims 1 to 13. 15. Device (1001, ..., 1007) according to claim 14, comprising: a gasification unit (10, 11) which is designed to receive an organic feedstock (1), wherein in particular a gasifier (10) of the gasification unit (10, 11) is designed to receive the organic feedstock (1), and by means of thermochemical conversion of the feedstock (1) to generate an untreated product gas (P1) containing carbon monoxide and hydrogen and a solid residue (P14), in particular a pyrolysis coke, wherein the device (1001, ..., 1007), in particular the gasification unit (10, 11), optionally further comprises a firing unit which is designed to burn at least a portion of the solid residue (P14) to generate a flue gas (P21) containing carbon dioxide, one or more treatment devices (20, 30, 40) which are designed to treat the untreated product gas (P1) to generate a treated product gas (P4) containing carbon monoxide and hydrogen, a water-gas shift reactor (50) which is designed to receive the treated product gas (P4) and water vapor (P8), and subjecting the treated product gas (P4) to a catalytically assisted water-gas shift reaction to obtain a conditioned product gas (P5) which has an increased hydrogen content compared to the treated product gas (P4) and contains carbon dioxide, at least one carbon dioxide separation system (60, 90) which is designed to receive the conditioned product gas (P5) and/or the flue gas (P21) and to separate carbon dioxide from the conditioned product gas (P5) and/or the flue gas (P21) in order to generate the carbon dioxide product stream (P11, P23), a hydrogen separation system (70) which is designed to receive at least a portion (P5, P6) of the conditioned product gas (P5) and to separate hydrogen from the at least a portion (P5, P6) of the conditioned product gas (P5) in order to generate the hydrogen product stream (P10), and a line arrangement which is designed to produce a residual gas (P13) containing carbon monoxide and hydrogen from the hydrogen separation system (70) into the gasification unit (10, 11), whereby the gasification unit (10, 11), in particular a combustion unit of the gasification unit (10, 11), is designed to thermally utilize the recycled residual gas (P13).