CN117623224A - Hydrocarbon fuel in-situ decarbonizing hydrogen production device and method - Google Patents
Hydrocarbon fuel in-situ decarbonizing hydrogen production device and method Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 104
- 239000001257 hydrogen Substances 0.000 title claims abstract description 104
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000000446 fuel Substances 0.000 title claims abstract description 45
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 345
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 239000003463 adsorbent Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000002407 reforming Methods 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 abstract description 28
- 238000005265 energy consumption Methods 0.000 abstract description 15
- 238000005262 decarbonization Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 238000006057 reforming reaction Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000005261 decarburization Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
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- 239000002918 waste heat Substances 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 3
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
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- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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Abstract
The invention provides a hydrocarbon fuel in-situ decarbonization hydrogen production device and a method, wherein the hydrocarbon fuel in-situ decarbonization hydrogen production device comprises: the first reaction group comprises a first reaction unit and a second reaction unit which are sequentially connected; the second reaction group is arranged in parallel with the first reaction group and comprises a third reaction unit and a fourth reaction unit which are sequentially connected; the product outlet of the first reaction unit and the product outlet of the third reaction unit are connected with the first product outlet pipeline; and the product outlet of the second reaction unit and the product outlet of the fourth reaction unit are connected with the second product outlet pipeline. Sequential separation of hydrogen from the product using two different product adsorbentsGas and carbon dioxide, reducing the separation resistance of products, improving the separation proportion and reducing the separation energy consumption. Simultaneously can realize the preparation of high-purity hydrogen and the high-concentration CO 2 Is a capture of (a).
Description
Technical Field
The invention relates to the technical field of hydrogen energy and carbon reduction, in particular to a hydrocarbon fuel in-situ decarburization hydrogen production device and method.
Background
Hydrogen energy is a secondary energy source with rich sources and wide application, and has become an important direction for low-carbon development and transformation of energy. Based on the premise that the short-term internal energy structure is difficult to radically reform, the reform technology is needed to promote the fossil energy hydrogen production technology, carbon fixation and emission reduction are achieved, the collaborative development of fossil energy and new energy is promoted, and a support is provided for constructing a safe, efficient and low-carbon clean energy system. The traditional fossil energy hydrogen production technology (such as methane reforming, methanol reforming and the like) has the defects that the required reaction temperature is high, the reaction heat absorption is supplied in a fuel combustion mode, the hydrogen production amount of unit raw materials (hydrocarbon fuel) is reduced, the corresponding energy consumption of unit hydrogen production is high, and the carbon emission is high. The temperature of the hydrogen production reaction is greatly reduced, and the waste heat can be used for replacing combustion, so that the consumption of raw materials (hydrocarbon fuel) is reduced, and the hydrogen production energy consumption and the carbon emission are reduced. Meanwhile, in order to obtain higher purity hydrogen, a pressure swing adsorption unit (PSA) is generally added to the conventional hydrogen production plant downstream of the reaction, which further increases the hydrogen production energy consumption and the complexity of the system. On the other hand, a large amount of CO is generated in the hydrogen production process 2 Is a smoke of the gas turbine. The trapping, the utilization and the sealing of the carbon dioxide are key technical means for realizing the sustainable development of an energy system. However, CO commonly used in industry such as amine decarbonization 2 The regeneration energy consumption of the trapping technology is higher, and the hydrogen production cost and the hydrogen production energy consumption are increased. At the same time, the additional carbon capture devices also complicate the system.
In order to break through the bottleneck, the hydrogen production method based on the in-situ separation of the product hydrocarbon fuel has certain advantages in reducing energy consumption, reaction temperature and hydrogen production equipment quantity. According to the Leschateri principle, after the products in the reaction system are separated, the reaction balance moves forward, so that the conversion rate of raw materials can be improved, and the reaction temperature can be reduced. Research at home and abroad mainly focuses on H based on hydrogen permeable membrane material 2 Separation enhancement techniques or basesCO in adsorbent material 2 Separation strengthening technology. However, in the above-described single product separation method, as one product is separated out, the concentration of the other product remaining in the reactor is excessively high, and further progress of the reaction is inhibited. Meanwhile, as the partial pressure of the separated product gradually decreases, the separation energy consumption increases sharply.
Patent CN105776133a discloses a methane reforming system in which methane and steam lines flow through a hydrogen separation device and a carbon dioxide separation device in sequence and form a cycle. In the system, the separation and beating circulation of the two products promote the forward movement of the balance of the methane reforming reaction, so that the methane conversion rate is greatly improved, and the problems of the separation of the single products are solved to a certain extent. However, in the separation device, the reaction process and the product separation process are performed in different chambers, so that the resistance to the movement of the target product is increased, the pressure distribution in the device is uneven, the driving force for separating the product is reduced, and the complete separation of the product is difficult to realize. Meanwhile, the method can realize high conversion rate of methane through a plurality of cycles, and when tail gas enters the next cycle, the driving force of a separation device is consumed in the previous cycle, so that the driving force of separation of products in the next cycle is reduced, and the effect of strengthening reaction of product separation is weakened. In the practical implementation of the system, due to the persistence and intermittence of the product separation process, the multistage circulation required to reach high conversion rate of methane cannot necessarily be performed at the same time, but must be performed sequentially with time sequence; this necessarily results in the system shown in the schematic diagram of the patent publication, in practical implementation, to add spatial auxiliary units (such as gas storage devices, circulation pipes, and connection modes thereof, etc.) not shown in the figure, so as to meet the timing requirement of implementing multiple cycles. Therefore, the patent publication only proposes a basic principle idea, but does not necessarily bring about the beneficial effect of high conversion of methane, and fails to explain how the effect of high conversion of methane is achieved in practical practice. In the case of an adsorbent-based, the separation device needs to be regenerated after the adsorbent is saturated, so that the method cannot realize a continuous and uniform hydrogen production process. Meanwhile, the heat source is always continuously input, and the contradiction between the intermittent reaction process and the continuous heat input can reduce the energy utilization efficiency of the system and increase the hydrogen production energy consumption.
Disclosure of Invention
In view of this, the present description examples provide a stable, continuous, one-step process for producing high purity hydrogen and capturing high concentration CO 2 The hydrocarbon fuel in-situ decarbonization hydrogen production device and method can reduce the temperature, heat supply energy consumption and carbon dioxide emission in the hydrocarbon fuel reforming process.
The embodiment of the specification provides the following technical scheme: an in-situ decarbonizing hydrogen production device for hydrocarbon fuel, comprising: the first reaction group comprises a first reaction unit and a second reaction unit which are sequentially connected; the second reaction group is arranged in parallel with the first reaction group and comprises a third reaction unit and a fourth reaction unit which are sequentially connected; the product outlet of the first reaction unit and the product outlet of the third reaction unit are connected with the first product outlet pipeline; and the product outlet of the second reaction unit and the product outlet of the fourth reaction unit are connected with the second product outlet pipeline.
Further, the hydrocarbon fuel in-situ decarbonizing hydrogen production device also comprises a tail gas pipeline, and the tail gas outlet of the first reaction group and the tail gas outlet of the second reaction group are connected with the tail gas pipeline.
Further, the first reaction units and the second reaction units are multiple, and the first reaction units and the second reaction units are alternately connected in series.
Further, the third reaction units and the fourth reaction units are multiple, and the third reaction units and the fourth reaction units are alternately connected in series.
Further, both the first product outlet line and the second product outlet line are provided with vacuum pumps.
Further, a pressurizing unit is provided in the first reaction set or in the second reaction set at the inlet line.
Further, the first reaction set and/or the second reaction set is provided with an external heating device.
Further, the first reaction group and the second reaction group are multiple, and the multiple first reaction groups and the multiple second reaction groups are arranged in parallel.
The invention also provides a hydrogen production method, which adopts the hydrocarbon fuel in-situ decarbonizing hydrogen production device to produce hydrogen, and comprises the following steps: a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units and a plurality of third reaction units; putting a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent into a plurality of second reaction units and a plurality of fourth reaction units; introducing reactant feedstock into the first reaction unit and the first third reaction unit; the first reaction units and the second reaction units are sequentially conducted, the last first reaction unit or the last second reaction unit is communicated with the tail gas pipeline, the third reaction units and the fourth reaction units are sequentially conducted, and the third reaction units or the fourth reaction units are communicated with the tail gas pipeline.
The invention also provides a hydrogen production method, which adopts the hydrocarbon fuel in-situ decarbonizing hydrogen production device to produce hydrogen, and comprises the following steps: a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units and a plurality of third reaction units; putting a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent into a plurality of second reaction units and a plurality of fourth reaction units; introducing a reactant feedstock into a first reaction unit; sequentially conducting a plurality of first reaction units and a plurality of second reaction units, and enabling the last first reaction unit or the last second reaction unit to be communicated with a tail gas pipeline; the third reaction units are communicated with the first product outlet pipeline, desorbed hydrogen flows out of the first product outlet pipeline, the fourth reaction units are communicated with the second product outlet pipeline, and desorbed carbon dioxide can flow out of the second product outlet pipeline.
The invention also provides a hydrogen production method, which adopts the hydrocarbon fuel in-situ decarbonizing hydrogen production device to produce hydrogen, and comprises the following steps: a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units and a plurality of third reaction units; putting a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent into a plurality of second reaction units and a plurality of fourth reaction units; passing a reactant feedstock to a first third reaction unit; sequentially conducting a plurality of third reaction units and a plurality of fourth reaction units, and enabling the last third reaction unit or the fourth reaction unit to be communicated with a tail gas pipeline; the first reaction units are communicated with the first product outlet pipeline, the desorbed hydrogen can flow out from the first product outlet pipeline, the second reaction units are communicated with the second product outlet pipeline, and the desorbed carbon dioxide can flow out from the second product outlet pipeline.
Compared with the prior art, the beneficial effects that above-mentioned at least one technical scheme that this description embodiment adopted can reach include at least:
(1) By reasonably arranging and regulating the flow control device among the reaction units, different adsorbents can be utilized to adsorb hydrogen and carbon dioxide in the product in the reaction stage sequence, and then high-purity hydrogen and high-concentration CO can be respectively obtained in the product desorption stage 2 Realizes the synergy of high-efficiency hydrogen production by fossil energy and carbon dioxide trapping and resource utilization.
(2) The product is adsorbed in situ in the reaction unit, so that the separation resistance of reactants can be reduced, the separation proportion is improved, and a more thorough product separation effect is realized. The adsorbent can generate larger heat effect in the adsorption and regeneration processes, can supply heat required by catalytic reaction, and reduces external energy input required by the reaction stage.
(3) The continuous preparation of hydrogen can be realized and the process stability is improved by connecting a plurality of groups of reaction units in parallel and relating to corresponding gas pipelines and reaction schemes. Different groups of reaction units are in different reaction stages, can mutually carry out heat complementation, improve the energy utilization efficiency, and simultaneously reduce the carbon emission generated by heat supply.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a set of reaction units in a reaction stage according to an embodiment of the invention;
FIG. 3 is a schematic flow diagram of a set of reaction units in a desorption stage according to an embodiment of the present invention;
FIG. 4 is a schematic illustration of the thermal complementation of the interior of a reaction unit according to an embodiment of the present invention.
Reference numerals in the drawings: 3. an inlet line; 4. a tail gas pipeline; 5. a first product outlet line; 6. a second product outlet line; 11. a first reaction unit; 12. a second reaction unit; 13. a flow controller on the connection line between the first group of reaction units; 14. a flow controller on the first set of first product outlet lines; 15. a flow controller on the first set of second product outlet lines; 21. a third reaction unit; 22. a fourth reaction unit; 23. a flow controller on the connecting line between the second group of reaction units; 24. a flow controller on the second set of first product outlet lines; 25. a flow controller on the second set of second product outlet lines.
Detailed Description
Embodiments of the present application are described in detail below with reference to the accompanying drawings.
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As shown in fig. 1, an embodiment of the present invention provides an in-situ decarbonizing hydrogen production device for hydrocarbon fuel, which comprises a first reaction group, a second reaction group, a first product outlet pipeline 5 and a second product outlet pipeline 6. Wherein the first reaction group comprises a plurality of first reaction units 11 and a plurality of second reaction units 12 which are sequentially connected; the second reaction group is arranged in parallel with the first reaction group, and comprises a plurality of third reaction units 21 and a plurality of fourth reaction units 22 which are sequentially connected; the product outlet of the first reaction unit 11 and the product outlet of the third reaction unit 21 are both connected with the first product outlet pipeline 5; the product outlet of the second reaction unit 12 and the product outlet of the fourth reaction unit 22 are both connected to the second product outlet line 6.
The hydrogen and the carbon dioxide in the products are sequentially separated by using two different product adsorbents, so that the forward movement of the reaction balance can be pushed, the separation energy consumption is reduced, and the conversion rate and the selectivity of reactants are improved. The hydrogen and the carbon dioxide are adsorbed in different reaction units, the connection state of the gas pipeline is changed through a flow controller, and the adsorbent is regenerated, so that high-purity hydrogen and high-concentration CO can be simultaneously obtained 2 Realizes the synergy of hydrogen production and fossil energy decarburization.
In the embodiment of the present invention, a flow controller 13 on a first group of inter-reaction unit connection lines is disposed between the first reaction unit 11 and the second reaction unit 12, a flow controller 14 on a first group of first product outlet lines is disposed between the first reaction unit 11 and the first product outlet line 5, and a flow controller 15 on a first group of second product outlet lines is disposed between the second reaction unit 12 and the second product outlet line 6.
A flow controller 23 on the second group of inter-reaction-unit connection lines is provided between the corresponding third reaction unit 21 and fourth reaction unit 22, a flow controller 24 on the second group of first product outlet lines is provided between the third reaction unit 21 and the first product outlet line 5, and a flow controller 25 on the second group of second product outlet lines is provided between the fourth reaction unit 22 and the second product outlet line 6.
Through setting up above-mentioned flow controller, can select different opening or closing state to realize the connection of different modes, and then reach the purpose that satisfies different operating mode demands.
The hydrocarbon fuel in-situ decarbonizing hydrogen production device also comprises a tail gas pipeline 4, and a tail gas outlet of the first reaction group and a tail gas outlet of the second reaction group are connected with the tail gas pipeline 4. In the embodiment of the present invention, the tail gas outlet of the first reaction group is the tail gas outlet of the last first reaction unit 11 or the second reaction unit 12. The tail gas outlet of the second reaction group is the tail gas outlet of the third reaction unit 21 or the fourth reaction unit 22 at the last.
The first reaction unit 11 and the second reaction unit 12 are different from each other, the third reaction unit 21 may be the same as the first reaction unit 11, and the fourth reaction unit 22 may be the same as the second reaction unit 12.
Of course, in another embodiment, the first reaction unit 11, the second reaction unit 12, the third reaction unit 21, and the fourth reaction unit 22 are all different. However, both the first reaction unit 11 and the third reaction unit 21 may produce a first product and both the second reaction unit 12 and the fourth reaction unit 22 may produce a second product.
In the embodiment of the invention, the first reaction unit 11 and the second reaction unit 12 are multiple, and the multiple first reaction units 11 and the multiple second reaction units 12 are sequentially connected in series. The third reaction unit 21 and the fourth reaction unit 22 are plural, and the plural third reaction units 21 and the plural fourth reaction units 22 are alternately arranged in series.
As shown in fig. 1, in this embodiment, the first reaction unit 11, the second reaction unit 12, the third reaction unit 21, and the plurality of fourth reaction units 22 are all three and are sequentially arranged. The number of the corresponding reaction units in each reaction group can be a base number or an even number, and the reaction units can be selected according to different requirements.
Preferably, in a not shown embodiment, a fifth reaction unit may be provided between the first reaction unit 11 and the second reaction unit 12. The fifth reaction unit may provide an auxiliary supporting function for the catalytic unit for smooth progress of the entire reaction apparatus.
Preferably, in an embodiment not shown, a pressurizing unit may be provided in the reaction group, and the pressurizing unit may allow the reaction unit to perform the reaction under a condition higher than the atmospheric pressure. The mounting location of the pressurizing unit may be selected according to different operating conditions, for example at the inlet line.
The first product outlet line 5 and the second product outlet line 6 are each provided with a vacuum pump. The provision of a vacuum pump allows for the withdrawal of the first product outlet line 5 and the second product outlet line 6, reducing the partial pressure of the products within the reaction unit, allowing the first product and the second product to desorb and rapidly flow out of the reaction unit. Although the vacuum pump in this embodiment reduces the partial pressure of the product in the product adsorption reactor, the invention is not limited thereto. The way to reduce the partial pressure of the product in the product adsorption reactor may also be to introduce an inert gas or steam into the reactor.
The reaction unit is provided with external heating devices which are independent of each other and can independently set heating temperature to meet different working condition demands.
The external heat supply device is used for providing heat for hydrocarbon fuel reforming reaction in the product adsorption reactor. The temperature required for the methanol reforming reaction is generally 200-350 ℃, and the temperature required for the methane reforming reaction is generally 400-800 ℃. Wherein, the heat energy source of the external heat supply device comprises any one or more of the following: combustion of methanol, methane or other fossil fuels, electrical heating, solar energy, industrial waste heat, biomass waste heat. When the device is combined with solar heat energy, industrial waste heat or biomass waste heat, the consumption of electric energy and fossil energy can be further reduced, the carbon emission in the hydrogen production process is reduced, and the device is cleaner and environment-friendly.
The individual external heating devices may allow for different operating conditions for each reaction unit, e.g. different reaction units operating at different operating temperatures; or different working steps (reaction, desorption) are run at different working temperatures. This allows the individual materials in the reaction unit to be operated at a suitable temperature.
The first reaction groups and the second reaction groups are all multiple, and the multiple first reaction groups and the multiple second reaction groups are arranged in parallel.
In the embodiment of the invention, by arranging a plurality of first reaction groups and a plurality of second reaction groups in parallel, each reaction group can be independently regarded as a reaction unit, namely the operation between the first reaction group and the second reaction group can be consistent or different. When the operations between the first reaction set and the second reaction set are opposite, the first reaction set and the second reaction set may be alternately operated, thereby enabling the hydrogen production reaction to be continuously operated.
In a first embodiment of the invention, not shown, the first 11 and third 21 reaction units of the apparatus described above are filled with a catalyst and one adsorbent, and the second 12 and fourth 22 reaction units are filled with another adsorbent.
In a second embodiment of the present invention, not shown, taking the first reaction set as an example, the plurality of first reaction units 11 and the plurality of second reaction units 12 form one subgroup, and two or more subgroups are provided in the reaction set for achieving the effect of sequentially separating the corresponding products.
In a third embodiment of the invention, not shown, a pressurizing unit is provided at the inlet line 3, which pressurizing unit allows the reaction unit to react at a pressure above atmospheric pressure and then to release the pressure. And each reaction unit can perform desorption of the product under normal pressure or vacuum conditions. Of course, the installation position of the pressurizing unit may be selected according to different working conditions, for example, the pressurizing unit is arranged in the first reaction group or the second reaction group, and all embodiments capable of achieving the above functions or effects are within the scope of protection of the present application.
Preferably, the embodiment of the invention also provides a hydrogen production method, which adopts the hydrocarbon fuel in-situ decarburization hydrogen production device to produce hydrogen, and comprises the following steps:
a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are placed in the first reaction unit 11 and the third reaction unit 21;
a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent are placed in the second reaction unit 12 and the fourth reaction unit 22;
passing reactant feedstock to a first reaction unit 11 and a first third reaction unit 21;
the first reaction units 11 and the second reaction units 12 are sequentially conducted, the last reaction unit is communicated with the tail gas pipeline 4, and the third reaction units 21 and the fourth reaction units 22 are sequentially conducted, and the last reaction unit is communicated with the tail gas pipeline 4.
Or the first reaction units 11 and the second reaction units 12 are sequentially conducted, the last reaction unit is communicated with the tail gas pipeline 4, the third reaction units 21 are communicated with the first product outlet pipeline 5, and the fourth reaction units 22 are communicated with the second product outlet pipeline 6.
Or the third reaction units 21 and the fourth reaction units 22 are sequentially conducted, the last reaction unit is communicated with the tail gas pipeline 4, the first reaction units 11 are communicated with the first product outlet pipeline 5, and the second reaction units 12 are communicated with the second product outlet pipeline 6.
It should be noted that the materials of the hydrogen adsorbent and the carbon dioxide adsorbent are well known to those skilled in the art, and only a few common materials are given here as examples. The hydrogen adsorbent material is selected from one of the following materials: hydrogen storage metal alloy, activated carbon, graphite nanofiber, carbon nanotube, etc. The carbon dioxide adsorbing material is selected from one of the following materials: hydrotalcite, activated carbon, lithium silicate adsorbent, and the like. Specific examples will be provided below for the detailed description of the present application.
In the embodiment of the invention, the catalyst and the adsorbent in the reaction unit are uniformly mixed and filled. Meanwhile, the mixing ratio of the two materials may be different in different first (or second) reaction units. For example, the catalyst/adsorbent mass ratio in each reaction unit may gradually decrease along the flow direction.
First embodiment: in this embodiment, the methanol reforming catalyst is CuO/ZnO/Al 2 O 3 Catalyst, hydrogen adsorbent is LaNi 4.3 Al 0.7 Alloy and carbon dioxide adsorbent is active carbon.
The chemical reaction formula of the methanol reforming reaction is shown in formula (I):
in this example, the first product is carbon dioxide and the second product is hydrogen. In the first reaction unit 11, the methanol reforming reaction catalyst and the carbon dioxide adsorbent are uniformly mixed and packed. In the second reaction unit 12, the methanol reforming reaction catalyst and the hydrogen adsorbent are uniformly mixed and packed. The mixing loading ratio of the catalyst and the adsorbent may be different in different reaction units.
Taking a group of reaction units as an example, the specific steps are as follows:
FIG. 2 is a schematic flow diagram of a set of reaction units in a reaction stage according to an embodiment of the invention. The methanol solution with a certain proportion is preheated and vaporized and then is introduced into the reaction units, and reactants sequentially flow through the first reaction unit 11 and the second reaction unit 12 which are sequentially connected. As the reactant flows through the first reaction unit 11, a methanol steam reforming reaction occurs, producing hydrogen and carbon dioxide. Meanwhile, the generated product carbon dioxide is adsorbed by the adsorbent activated carbon in situ. Adsorption separation of carbon dioxide promotes forward movement of the methanol steam reforming reaction and increases H in the remaining gas component 2 Partial pressure. As the reactant flows through the second reaction unit 12, a methanol steam reforming reaction occurs while the product hydrogen is being LaNi 4.3 Al 0.7 Alloy adsorption promotes forward movement of the methanol steam reforming reaction and increases CO in the residual gas component 2 Partial pressure. After passing through six alternating reaction units, the tail gas flows out of the reaction system through a tail gas pipeline 4.
FIG. 3 is a schematic flow diagram of a set of reaction units in a desorption stage according to an embodiment of the present invention. The methanol solution is stopped from being fed, the flow controller 13 on the connecting pipeline between the first group of reaction units between the first reaction unit and the second reaction unit is closed, and the valve on the first product outlet pipeline 5 and the valve on the second product outlet pipeline 6 are opened. All reactors are sequentially connected to form a connection mode that the same product adsorption reaction units are communicated with each other, and different product adsorption reaction units are separated.
The first product outlet pipeline 5 and the second product outlet pipeline 6 are respectively connected with two vacuum pumps, and the vacuum pumps are operated under isothermal conditions, so that the partial pressure in the product adsorption reaction unit is reduced, and the regeneration of the adsorbent is realized. Meanwhile, because the two product separation reactors are separated from each other in space, high-purity hydrogen and high-concentration CO can be respectively obtained 2 Realizes the synergistic effect of decarburization and hydrogen production.
After the regeneration of the adsorbent is completed, the valves on the first product outlet line 5 and the second product outlet line 6 are closed, and the flow controllers 13 on the first group of inter-reaction-unit connection lines are opened. The state of all the reaction units connected sequentially is restored to start the next cycle.
In this embodiment, two parallel reaction sets are provided. When one group is in the adsorbent regeneration step, the other group is in the methanol steam reforming reaction and pipeline adjustment stage. The two reaction groups alternately regenerate the hydrogen adsorbent in sequence under normal operation, so that the reaction system continuously prepares hydrogen.
The present embodiment does not include a pressurizing step. When the pressure needs to be increased to improve the reaction effect of the adsorption separation reactor, the step of increasing and reducing the pressure is generally added in the step, and at this time, the continuous production of the hydrogen can be realized by connecting more groups of reactors in parallel corresponding to different reaction steps.
Due to the hydrogen in the Lani 5 The heat of adsorption in the material is about 29-32kJ/mol. The required heat absorption for complete reaction of 1mol of methanol was 49.4kJ, and 3mol of hydrogen produced was subjected to LaNi 5 The exotherm of the material adsorption is about 87-96kJ. In the case of homogeneous mixing of the catalyst and the adsorbent, the reaction stage can be substantially autothermal, as shown in fig. 4. Meanwhile, if the 2 groups of reactors connected in parallel are reasonably arranged, the reactors in the reaction stage can also provide partial heat for the endothermic desorption reaction in the other group of reactors, so that higher energy utilization efficiency is obtained.
Second embodiment: in this embodiment, the methane reforming catalyst selected is Ni/Al 2 O 3 Catalyst, hydrogen adsorbent is LaNi 4.3 Al 0.7 The alloy and the carbon dioxide adsorbent are lithium silicate.
The chemical reaction formula of the methane reforming reaction is shown as a formula (II):
CH 4 +2H 2 O＝4H 2 +CO 2 (II)
In this embodiment, two sets of parallel decarburization hydrogen production reaction sets are provided. Four first reaction units 11 and four second reaction units 12 are provided in each reaction group. The first product is carbon dioxide and the second product is hydrogen. In the first product adsorption reactor, the methane reforming reaction catalyst and the carbon dioxide adsorbent are uniformly mixed and filled. In the second product adsorption reactor, the methane reforming reaction catalyst and the hydrogen adsorbent are uniformly mixed and filled. The mixing loading ratio of the catalyst and the adsorbent may be different in different reactors.
The energy consumption analysis and comparison of the conventional methane steam reforming hydrogen production, in-situ decarbonizing hydrogen production of this example, are shown in table 1 below. Analysis results show that compared with the traditional methane steam reforming hydrogen production, the methane reforming method based on in-situ hydrogen production decarburization can consume methane from 5.38m per 1kg of hydrogen 3 Reduced to 4.36m 3 The energy saving rate reaches 18.9 percent.
TABLE 1 energy consumption analysis and comparison
In the energy consumption analysis, the heat required by the methane reforming reaction based on in-situ hydrogen production decarburization is provided by natural gas combustion, and if the heat is changed into heat supply by heat sources such as concentrated solar heat energy, industrial waste heat or biomass waste heat, the natural gas energy consumption in the process can be further reduced.
The foregoing description of the embodiments of the invention is not intended to limit the scope of the invention, so that the substitution of equivalent elements or equivalent variations and modifications within the scope of the invention shall fall within the scope of the patent. In addition, the technical characteristics and technical scheme, technical characteristics and technical scheme can be freely combined for use.
Claims (11)
1. An in situ decarbonizing hydrogen production device for hydrocarbon fuel, which is characterized by comprising:
the first reaction group comprises a first reaction unit (11) and a second reaction unit (12) which are connected in sequence;
the second reaction group is arranged in parallel with the first reaction group and comprises a third reaction unit (21) and a fourth reaction unit (22) which are sequentially connected;
the first product outlet pipeline (5), the product outlet of the first reaction unit (11) and the product outlet of the third reaction unit (21) are connected with the first product outlet pipeline (5);
and a second product outlet pipeline (6), wherein a product outlet of the second reaction unit (12) and a product outlet of the fourth reaction unit (22) are connected with the second product outlet pipeline (6).
2. The hydrocarbon fuel in-situ decarbonizing hydrogen production device according to claim 1, further comprising a tail gas pipeline (4), wherein the tail gas outlet of the first reaction group and the tail gas outlet of the second reaction group are both connected with the tail gas pipeline (4).
3. The hydrocarbon fuel in-situ decarbonizing hydrogen production device according to claim 1, wherein the first reaction unit (11) and the second reaction unit (12) are plural, and the plural first reaction units (11) and the plural second reaction units (12) are alternately arranged in series.
4. The hydrocarbon fuel in-situ decarbonizing hydrogen production device according to claim 1, wherein the third reaction unit (21) and the fourth reaction unit (22) are plural, and the plural third reaction units (21) and the plural fourth reaction units (22) are alternately arranged in series.
5. The hydrocarbon fuel in-situ decarbonizing hydrogen production device according to claim 1, characterized in that the first product outlet line (5) and the second product outlet line (6) are each provided with a vacuum pump.
6. Hydrocarbon fuel in situ decarbonizing hydrogen plant according to claim 1, characterized in that a pressurizing unit is provided in the first reaction group or in the second reaction group at the inlet line (3).
7. The hydrocarbon fuel in-situ decarbonizing hydrogen plant of claim 1, wherein the first reaction set and/or the second reaction set is provided with an external heating device.
8. The hydrogen plant for in-situ decarbonizing of hydrocarbon fuels according to any one of claims 1 to 7, wherein the first reaction group and the second reaction group are plural, and the plural first reaction groups and the plural second reaction groups are arranged in parallel.
9. A hydrogen production method using the hydrocarbon fuel in-situ decarbonizing hydrogen production apparatus as claimed in any one of claims 1 to 8, characterized by comprising:
a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units (11) and a plurality of third reaction units (21);
a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent are put into a plurality of second reaction units (12) and a plurality of fourth reaction units (22);
introducing reactant feedstock into a first reaction unit (11) and a first third reaction unit (21);
sequentially conducting a plurality of first reaction units (11) and a plurality of second reaction units (12), and enabling the last first reaction unit (11) or the last second reaction unit (12) to be communicated with a tail gas pipeline (4);
simultaneously, a plurality of third reaction units (21) and a plurality of fourth reaction units (22) are sequentially conducted, and the last third reaction unit (21) or the fourth reaction unit (22) is communicated with the tail gas pipeline (4).
10. A hydrogen production method using the hydrocarbon fuel in-situ decarbonizing hydrogen production apparatus as claimed in any one of claims 1 to 8, characterized by comprising:
a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units (11) and a plurality of third reaction units (21);
a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent are put into a plurality of second reaction units (12) and a plurality of fourth reaction units (22);
introducing a reactant feedstock into a first reaction unit (11);
the first reaction units (11) and the second reaction units (12) are sequentially conducted, and the last first reaction unit (11) or the second reaction unit (12) is communicated with the tail gas pipeline (4);
communicating a plurality of third reaction units (21) with the first product outlet pipeline (5) and enabling desorbed hydrogen to flow out of the first product outlet pipeline (5);
a plurality of fourth reaction units (22) are communicated with the second product outlet pipeline (6) and can enable desorbed carbon dioxide to flow out of the second product outlet pipeline (6).
11. A hydrogen production method using the hydrocarbon fuel in-situ decarbonizing hydrogen production apparatus as claimed in any one of claims 1 to 8, characterized by comprising:
a hydrocarbon fuel reforming catalyst and a hydrogen adsorbent are put into a plurality of first reaction units (11) and a plurality of third reaction units (21);
a hydrocarbon fuel reforming catalyst and a carbon dioxide adsorbent are put into a plurality of second reaction units (12) and a plurality of fourth reaction units (22);
passing a methanol solution into a first third reaction unit (21);
sequentially conducting a plurality of third reaction units (21) and a plurality of fourth reaction units (22), wherein the last third reaction unit (21) or the fourth reaction unit (22) is communicated with an exhaust pipeline (4);
communicating a plurality of first reaction units (11) with the first product outlet pipeline (5) and enabling desorbed hydrogen to flow out of the first product outlet pipeline (5);
a plurality of second reaction units (12) are communicated with the second product outlet pipeline (6) and can enable desorbed carbon dioxide to flow out of the second product outlet pipeline (6).
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