CN113753857B - Technology for preparing high-purity hydrogen by reforming coupling chemical chains of methane-containing combustible gas and application - Google Patents
Technology for preparing high-purity hydrogen by reforming coupling chemical chains of methane-containing combustible gas and application Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 156
- 239000007789 gas Substances 0.000 title claims abstract description 152
- 239000001257 hydrogen Substances 0.000 title claims abstract description 152
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 145
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000002407 reforming Methods 0.000 title claims abstract description 75
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 238000010168 coupling process Methods 0.000 title claims abstract description 13
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 238000005516 engineering process Methods 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 101
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 96
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000001301 oxygen Substances 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 48
- 238000006722 reduction reaction Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 22
- 239000002918 waste heat Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006057 reforming reaction Methods 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 230000009467 reduction Effects 0.000 description 20
- 238000002485 combustion reaction Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910002845 Pt–Ni Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The application discloses a process for preparing high-purity hydrogen by reforming coupling chemical chains of methane-containing combustible gas and application thereof, wherein the process comprises a reforming reactor, a hydrogen production reactor and a controller; the reforming reactor includes a first inlet conduit and a first exhaust conduit configured to communicate the reforming reactor and the hydrogen production reactor; the hydrogen production reactor comprises a second air inlet pipeline and a second air outlet pipeline; the hydrogen production reactor contains an oxygen carrier, and the reforming reactor contains a reforming catalyst; the controller controls the gas entering the hydrogen production reactor; the controller is used for switching the gas entering the hydrogen production reactor so that two chemical reactions are completed in the hydrogen production reactor; or three chemical reactions are completed in the hydrogen production reactor, and the controller controls the reaction to be circularly carried out. The process has high hydrogen purity, low carbon content, simple operation,High efficiency, etc.
Description
Technical Field
The present invention relates to, but is not limited to, the field of clean energy and thermochemical hydrogen production, and in particular to, but is not limited to, a methane-containing combustible gas hydrogen production process and application.
Background
Hydrogen is used as a chemical raw material and an energy carrier, and compared with other fuels, the hydrogen can not generate CO when being used 2 Etc., and thus hydrogen energy is an important medium for achieving the global "carbon neutralization" objective in the future. However, hydrogen is usually present in the environment in the form of compounds such as H 2 O or C n H m The preparation of elemental hydrogen requires a relatively large amount of energy. In addition, the hydrogen fuel cell is used as an important hydrogen unit, and the purity requirement of the hydrogen is generally more than or equal to 99.9%, so that the technology for efficiently preparing the high-purity hydrogen becomes to realize the hydrogen energy scaleThe popularization and application are very important.
The mature process route in the prior hydrogen production technology is a combined process of reforming natural gas and steam, and then carrying out water gas shift and pressure swing adsorption separation. However, the energy structure of rich coal, short oil and less gas in China is not suitable for developing natural gas to prepare hydrogen. In contrast, china has rich coal-based synthesis gas and biomass fuel gas, and hydrogen can be prepared by utilizing the gas. Coal-based synthesis gas and biomass gas are used as mixed gas, and are usually CH 4 、CO 2 、H 2 And CO predominate. Although these gases can be converted to H by steam reforming 2 And CO, and then converted to H by water gas 2 And CO 2 And finally preparing the high-purity hydrogen from the obtained gas through processes such as purification, decarbonization and the like. However, due to the long technical route, gas purification process and CO 2 The trapping energy consumption is higher, and the hydrogen production cost is greatly increased.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
Aiming at the problems of complex preparation process, low product purity and the like of the existing high-purity hydrogen, the application provides a device and a method for preparing high-purity hydrogen by coupling methane-containing combustible gas reforming with chemical chains and a methane-containing combustible gas reforming catalyst, which can be used for preparing high-purity hydrogen on one hand and realizing low-cost CO on the other hand 2 Capturing and recovering heat energy.
The application provides a device for preparing high-purity hydrogen, which comprises a reforming reactor, a hydrogen production reactor and a controller; the reforming reactor includes a first inlet conduit and a first exhaust conduit configured to communicate the reforming reactor and the hydrogen production reactor; the hydrogen production reactor comprises a second air inlet pipeline and a second air outlet pipeline;
the hydrogen production reactor contains an oxygen carrier, and the reforming reactor contains a reforming catalyst; the controller controls the gas entering the hydrogen production reactor;
the controller is used for switching the gas entering the hydrogen production reactor so that two chemical reactions are completed in the hydrogen production reactor, wherein the chemical reactions are an oxygen carrier reduction reaction and a steam hydrogen production reaction, and the controller controls the two reactions to be circularly carried out;
or alternatively, the first and second heat exchangers may be,
the controller is used for switching the gas entering the hydrogen production reactor so that three chemical reactions are completed in the hydrogen production reactor, wherein the chemical reactions are an oxygen carrier reduction reaction, a steam hydrogen production reaction and an oxygen carrier oxidation reaction, and the controller controls the two reactions to be carried out circularly.
The catalyst is utilized in the reforming reactor and converted, the biomass-based combustible gas is used as the raw material of the reforming reactor, and the prepared reformed gas is used for reducing the oxygen carrier in the reduction reactor of the chemical-looping hydrogen production reactor. Simultaneous reformed gas oxidation to CO 2 And water, CO after simple cooling at the gas outlet 2 And collecting, sealing and utilizing.
In one embodiment provided herein, the controller controls the gas entering the hydrogen production reactor to be the gas produced by the reforming reactor when the hydrogen production reactor is performing an oxygen carrier reduction reaction;
when the hydrogen production reactor performs the steam hydrogen production reaction, the controller controls the gas entering the hydrogen production reactor to be steam;
when the hydrogen production reactor performs the oxidation reaction of the oxygen carrier, the controller controls the gas entering the hydrogen production reactor to be air or oxygen.
In one embodiment provided herein, the hydrogen production reactors have more than two hydrogen production reactors, and the number of hydrogen production reactors is not less than the number of chemical reactions that need to be performed in the hydrogen production reactors.
In one embodiment provided herein, the controller is configured to switch gases into different hydrogen production reactors that are capable of producing hydrogen without interruption so that different reactions are performed simultaneously.
In one embodiment provided in the present application, the apparatus for preparing high purity hydrogen further includes an air inlet end air path switching system and an exhaust end air path switching system;
the controller controls the air inlet end air path switching system and the tail gas end air path switching system; the gas inlet end gas circuit switching system is communicated with the hydrogen production reactor and is configured to introduce gas into the hydrogen production reactor;
the tail gas end gas circuit switching system is communicated with the hydrogen production reactor and is configured to discharge gas in the hydrogen production reactor out of the hydrogen production reactor;
at the same time, the hydrogen production reactor is respectively in different reaction stages under the control of the controller, the air inlet end air path switching system and the tail gas end air path switching system;
at different moments, the same fixed bed reactor is in different reaction states under the control of the controller, the air inlet end air path switching system and the tail gas end air path switching system.
In one embodiment provided herein, the apparatus may further include a waste heat recovery unit; optionally, the preheating separator comprises at least one gas-liquid separator, at least one cooler and at least one waste heat boiler; optionally, the heat of the hydrogen production reactor and/or the heat of the reforming reactor is recovered by a preheat recovery unit.
In one embodiment provided herein, the oxygen carrier comprises one or more of molybdenum, germanium, tungsten, and iron; alternatively, the oxygen carrier used for the first charge may be a fully oxidized oxide of one or more of molybdenum, germanium, tungsten, iron. The above metal simple substance is also possible, and the reformed gas is used for reducing oxides possibly existing in the metal simple substance.
In one embodiment provided herein, the oxygen carrier has an average particle size of 1mm to 10mm.
In one embodiment provided herein, the reforming reactor contains a reforming catalyst; molecular oxygen reacts with the oxygen carrier and is converted into lattice oxygen to participate in the reaction. The oxygen carrier performs an oxygen-losing cycle.
Is proposed in the present applicationIn one embodiment, the reforming catalyst is selected from Ni/MgO, ni/Al 2 O 3 、Ni/CeO 2 、Ni/TiO 2 、Ni/Fe 2 O 3 、Ni/SiO 2 、Pt/MgO、Pt/Al 2 O 3 、Pt/CeO 2 、Pt/TiO 2 、Pt/Fe 2 O 3 、Pt/SiO 2 、NiPt/MgO、NiPt/Al 2 O 3 、NiPt/CeO 2 、NiPt/TiO 2 、NiPt/Fe 2 O 3 And NiPt/SiO 2 Any one or more of the following;
in one embodiment provided herein, the MgO, al 2 O 3 、CeO 2 、TiO 2 、Fe 2 O 3 、SiO 2 The catalyst is a carrier, ni element and Pt element are active components, the active components are attached to the carrier, the Pt element in the active components accounts for 1 to 3 percent of the weight of the carrier according to the weight content of the final reforming catalyst, and the Ni element in the active components accounts for 5 to 20 percent of the weight of the carrier.
In one embodiment provided herein, the reforming catalyst has an average particle size of 0.45mm to 2mm.
In one embodiment provided herein, the inlet end of the reforming reactor (gas furnace system) may be fed with a methane-containing combustible gas, and the reforming reactor atmosphere may be adjusted if desired, for example, fed with H 2 Steam, CO 2 Or O 2 The catalyst is used for activating or regenerating the reforming reaction, improving the efficiency of the reforming reactor and adjusting the gas proportion in the reforming reactor.
In one embodiment provided herein, the inlet end of the reforming reactor (gas furnace system) may be fed with a methane-containing combustible gas, and the reforming reactor atmosphere may be adjusted if desired, for example, fed with H 2 Steam, CO 2 Or O 2 The catalyst is used for activating or regenerating the reforming reaction, improving the efficiency of the reforming reactor and adjusting the gas proportion in the reforming reactor.
In yet another aspect, the present application provides a chemical looping hydrogen production process, using the apparatus described above, comprising the steps of:
first, a methane-containing combustible gas and CO 2 Reforming is carried out to generate reformed gas;
secondly, reducing the oxygen carrier by the reformed gas, and then, reacting the oxygen carrier with steam to produce hydrogen, wherein the oxygen carrier is thoroughly oxidized and reduced to complete a cycle;
or alternatively, the first and second heat exchangers may be,
secondly, reducing the oxygen carrier by the reformed gas, then, reacting the oxygen carrier with steam to produce hydrogen, and finally, further oxidizing the oxygen carrier, wherein the oxygen carrier is thoroughly oxidized to be reduced at the moment, so that one cycle is completed;
in one embodiment provided herein, the CO is generated after the CO is reacted with the oxygen carrier 2 Participating in the reforming of the methane-containing combustible gas, the H 2 H formed after reaction with oxygen carrier 2 O reacts with the oxygen carrier and steam to produce hydrogen;
in one embodiment provided herein, the reforming reaction, the oxygen carrier reduction reaction, the steam hydrogen production reaction, and the oxygen carrier oxidation reaction are each performed in different reactors.
In one embodiment provided herein, the reaction temperature of the oxygen carrier reduction reaction, the water vapor hydrogen production reaction, and the oxygen carrier oxidation reaction is 570 ℃ to 1000 ℃;
in one embodiment provided herein, the reaction pressure of the oxygen carrier reduction reaction, the water vapor hydrogen production reaction, and the oxygen carrier oxidation reaction is from atmospheric pressure to 3MPa.
For hydrogen production reactors, no special calibration of water vapor flow and air flow is required, as both reactions are not kinetically controlled.
In one embodiment provided herein, the reforming reaction has a reaction temperature of 500 ℃ to 1000 ℃;
in one embodiment provided herein, the reaction pressure of the reforming reaction is normal pressure;
in one embodiment provided herein, the methane-containing combustible gas has a flow rate, mass space velocity of 6L g -1 h -1 To 12L g -1 h -1 ；
In one embodiment provided herein, the methane-containing combustible gas includes any one or more of biogas, biomass pyrolysis gas, coal-based syngas, and natural gas;
in one embodiment provided herein, the methane-containing combustible gas contains CO 2 A volume fraction of 10vol.% to 80vol.% and a volume fraction of methane of 20% to 70%;
in one embodiment provided herein, the balance gas comprises H 2 、CO、C 2 H 4 And C 2 H 6 Any one or more of, preferably, the C 2 H 4 And C 2 H 6 Less than 5vol.% of one or both of (c). The application provides a device for preparing high-purity hydrogen, wherein the reactor takes combustible gas containing methane as a raw material, and the device for preparing high-purity hydrogen comprises a hydrogen production reactor;
the device and the method for preparing high-purity green hydrogen by using the biomass gas reforming coupling chemical chain provided by the application achieve the following technical effects:
1. the methane-containing combustible gas directly enters a reforming reactor, and CH is converted by a reforming catalyst 4 And CO 2 Converted into synthesis gas in reforming reactor CH 4 And CO 2 The conversion rate reaches 95% and 90% respectively. And simultaneously, the problem of hydrogen purity reduction caused by carbon in the oxygen carrier is avoided.
2. The reformed fuel gas is mainly composed of synthesis gas (H 2 And CO) is the main component, the reaction rate of the coupling process and the oxygen carrier is far higher than that of methane, so that the reaction efficiency of the coupling process is greatly improved, and the coupling process are simultaneously used for preparing the H-containing gas in a chemical-looping hydrogen production reactor 2 The product is simply condensed and dehydrated to obtain high-purity H 2 The purity is more than or equal to 99 percent, a complex gas purifying device is not needed, the operation is simple, and the hydrogen production cost is low. In addition, deep reduction can be realized, and the actual hydrogen production is approximately equal to the theoretical hydrogen production of the oxygen carrier (0.37 m 3 /kg-Fe 2 O 3 )。
3. Reduction of oxygen carrierThe hydrogen production by steam and the oxidation stage of the oxygen carrier are spatially separated, so that CO generated in the reduction stage of the oxygen carrier can be avoided 2 The purity is more than or equal to 99 percent, and the system is ensured to have high carbon trapping efficiency;
4. the application uses CH 4 、H 2 Simultaneously with CO, part of CO 2 Converting into CO for utilization and simultaneously carrying out CO 2 The high-purity hydrogen prepared by the method has the characteristic of low carbon;
5. the chemical-looping hydrogen production reactor obtains the target product and simultaneously the tail gas at the outlet enters the waste heat recovery unit for waste heat recovery, so that the energy efficiency of the system is improved.
6. The conditions of each reactor are independently controlled, the operation is flexible, the efficiency is high, and the operation is safe and reliable.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the present application may be realized and attained by the structure particularly pointed out in the written description.
Drawings
The accompanying drawings are included to provide an understanding of the technical aspects of the present application, and are incorporated in and constitute a part of this specification, illustrate the technical aspects of the present application and together with the examples of the present application, and not constitute a limitation of the technical aspects of the present application.
FIG. 1 is a schematic diagram of a device for preparing high purity hydrogen by reforming coupling chemical chains of methane-containing combustible gas.
In fig. 1, the reference numerals are as follows: a-methane-containing combustible gas reforming reactor; b-chemical-looping hydrogen production reactor; a C-waste heat recovery unit; a 101-fixed bed reforming reactor; 102-a methane-containing gas delivery conduit; 103-Nitrogen or air or steam or CO 2 A delivery tube; 104-a hydrogen delivery pipe; 105-methane-containing combustible gas inlet control valve; 106-Nitrogen or air or steam or CO 2 An inlet control valve; 107-hydrogen inlet control valve; 108-a tail gas control valve after methane-containing combustible gas is reformed; 109-a methane-containing combustible gas reformed gas delivery conduit; 110-a fixed bed reforming reactor tail gas control valve; 111-fixed bed weightA tail gas discharge pipe of the whole reactor;
201-fixed bed reactor I; 202-fixed bed reactor II; 203-fixed bed reactor III;204—a water vapor inlet header; 205-air inlet manifold; 206-fixed bed reactor I air inlet control valve; 207-fixed bed reactor I steam inlet control valve; 208-a reformed gas inlet control valve of the fixed bed reactor I; 209-fixed bed reactor II air inlet control valve; 210-a fixed bed reactor II water vapor inlet control valve; 211-a reformed gas inlet control valve of a fixed bed reactor II; 212-fixed bed reactor III air inlet control valve; 213-fixed bed reactor III water vapor inlet control valve; 214-a fixed bed reactor III reformed gas inlet control valve;
215-a tail gas control valve of an air oxidation stage of the fixed bed reactor I; 216-a tail gas control valve of a steam oxidation hydrogen production stage of a fixed bed reactor I; a tail gas control valve after the oxygen carrier is reduced in the 217-fixed bed reactor I; 218-a tail gas control valve of an air oxidation stage of a fixed bed reactor II; 219-a tail gas control valve in a steam oxidation hydrogen production stage of a fixed bed reactor II; 220-a tail gas control valve after reduction of the oxygen carrier of the fixed bed reactor II; 221-a tail gas control valve of a III air oxidation stage of the fixed bed reactor; 222-a tail gas control valve of a steam oxidation hydrogen production stage of a fixed bed reactor III; 223-a tail gas control valve after reduction of the oxygen carrier of the fixed bed reactor III; 224-an oxygen carrier reduction stage tail gas delivery pipe; 225-a tail gas conveying pipe in the hydrogen production stage of steam oxidation; 226-an air oxidation stage tail gas delivery pipe;
301-an oxygen carrier reduction stage waste heat recovery unit; 302-a waste heat recovery unit in the hydrogen production stage of steam oxidation; 303-an oxygen carrier air oxidation stage waste heat recovery unit; 304-a boiler water inlet header pipe; 305-circulating cooling water inlet header pipe; 306-a condensate outlet header; 307-an exhaust gas discharge pipe; 308-H 2 A delivery tube; 309-CO 2 A delivery tube; 310-a waste heat recovery device steam header pipe; 311-circulating cooling water outlet header pipe.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the embodiments of the present application are described in detail below. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The present invention will be described in further detail below with reference to the drawings, but is not limited thereto.
As shown in FIG. 1, in a preferred embodiment of the invention, a device for preparing high-purity hydrogen by reforming coupling a methane-containing combustible gas with a chemical chain comprises a methane-containing combustible gas reforming reactor A, a chemical chain hydrogen production reactor B and a waste heat recovery unit C;
the specific process comprises the following steps:
step 1: firstly, valves 106 and 110 are opened, the rest valves are kept closed, nitrogen or other inert atmosphere gas is introduced through a pipeline 103, the fixed bed reforming reactor 101 is heated to a proper temperature of 500-1000 ℃ under the inert atmosphere, the temperature is maintained, after the temperature is constant, the valve 106 is closed, the valve 107 is opened, hydrogen is introduced into the catalyst to activate, after the activation is finished, the valve 107 is closed, and nitrogen is continuously introduced into the reactor to purge. At the same time, the fixed bed reactors I, II, III began to warm up to a constant 570℃to 1000℃and this temperature was maintained.
Step 2:2.1 Opening valves 105, 108, 208 and 217, closing all the other valves, introducing methane-containing combustible gas into the fixed bed reforming reactor 101 through a pipeline 102, and conveying the reformed gas of the fixed bed reforming reactor 101 to the fixed bed reactor I201 through a pipeline 109 for carrying out oxygen carrier reduction reaction (at this time, oxygen in the oxygen carrier participates in the reaction, and tail gas generated by the reaction can be condensed and trapped into pure CO through the generated water vapor) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Valves 208 and 217 are closed after the oxygen carrier reduction reaction is complete (i.e., when the reformate gas begins to penetrate the bed);
2.2 Valves 207, 216, 211, and 220 are opened, at which time a steam oxidation hydrogen production reaction (reaction tail gas can collect high purity hydrogen by condensation) occurs in fixed bed reactor I201, while an oxygen carrier reduction reaction occurs in fixed bed reactor II 202; closing valves 207, 216, 211 and 220 when the steam oxidation hydrogen production reaction in 201 and the oxygen carrier reduction reaction in 202 are finished;
2.3 Opening valves 206, 215, 210, 219, 214, and 223, and closing valves 206, 215, 210, 219, 214, and 223 at the end of the air oxidation reaction in fixed bed reactor I201, the steam oxidation hydrogen production reaction in fixed bed reactor II202, and the oxygen carrier reduction reaction in fixed bed reactor III 203;
2.4 Opening valves 208, 217, 209, 218, 213 and 222, and the fixed bed reactor I201 enters the next cycle to start the oxygen carrier reduction reaction, at this time, the fixed bed reactor II202 performs the air oxidation reaction, the fixed bed reactor III203 performs the steam oxidation hydrogen production reaction, and at the end of the reaction, the valves 208, 217, 209, 218, 213 and 222 are closed.
2.5 Valves 207, 216, 211 and 220, 212 and 221 are opened, the fixed bed reactor I201 starts the next cyclic steam oxidation hydrogen production reaction, at this time, the fixed bed reactor II202 undergoes the oxygen carrier reduction reaction, the fixed bed reactor III203 undergoes the air oxidation reaction, and at the end of the reaction, the valves 207, 216, 211 and 220, 212 and 221 are closed.
By repeating the step 2, the fixed bed reactors 201, 202 and 203 are controlled by the gas inlet end gas circuit control system and the tail gas short gas circuit switching system to be respectively in any one of the oxygen carrier reduction reaction, the water vapor oxidation hydrogen production reaction and the oxygen carrier air oxidation reaction at the same time, and the reactions carried out by different reactors at the same time are different, so that the continuous hydrogen production can be ensured.
The step 2 is performed while the waste heat recovery unit 301 in the oxygen carrier reduction stage, the waste heat recovery unit 302 in the water vapor oxidation hydrogen production stage, and the waste heat recovery unit 303 in the oxygen carrier air oxidation stage are performed to recover waste heat.
The methane-containing combustible gas can realize continuous high-purity hydrogen preparation through the reforming reactor and the chemical-looping hydrogen production reactor, thereby reducing the complex purification process in the traditional hydrogen production process and realizing CO at the same time 2 And the energy efficiency of the system is improved by capturing and waste heat recovery.
Example 1
The embodiment provides a method for preparing high-purity hydrogen by coupling methane-containing combustible gas reforming with a chemical chain and a methane-containing combustible gas reforming catalyst, as shown in fig. 1, wherein methane-containing combustible gas is reformed in a fixed bed reforming reactor, and then reformed gas is used as fuel of the chemical chain hydrogen production reactor to prepare high-purity hydrogen, and the method comprises the following steps:
the preparation method of the reforming catalyst in the invention specifically comprises the following steps: the water absorption of the commercial MgO powder was first determined to be 4.72mL/g MgO. According to Pt: (Pt+Ni+MgO) 1% by mass, ni: the method comprises the steps of weighing corresponding nickel nitrate hexahydrate and chloroplatinic acid with the mass percentage of (Pt+Ni+MgO) being 10%, preparing a solution with corresponding deionized water, mixing the salt solution with MgO powder at room temperature after dissolution, continuously stirring for 2-4 hours by using a glass rod, aging for 24 hours at room temperature, drying for 24 hours at 105 ℃, finally roasting for 4 hours at 850 ℃ in a muffle furnace air atmosphere, cooling and grinding to obtain the Pt-Ni/MgO catalyst, wherein the average particle size of the reforming catalyst is 0.45-2 mm.
In this example, the iron-based oxygen carrier is iron oxide (ferric oxide, purity 99%, average particle size 1mm to 10 mm); the iron agent oxygen carrier is filled in the fixed bed reactor I, the fixed bed reactor II and the fixed bed reactor III.
Filling the Pt-Ni/MgO catalyst in the invention into a fixed bed reforming reactor 101, opening valves 106 and 110, introducing nitrogen to maintain the inert atmosphere of the reactor, and heating the fixed bed reforming reactor 101 to 850 ℃ while the rest valves are kept closed; after the temperature is constant, closing the valve 106, opening the valve 107, and introducing hydrogen to activate the catalyst for 1h; closing valve 107, opening valve 106, purging for 30min, heating fixed bed reactor I201, fixed bed reactor II202 and fixed bed reactor III203 to 850 deg.C, opening valves 105, 108, 208 and 217 after the temperature is constant, closing all the other valves, and pumping biogas (CH in biogas) via 102 lines 4 Volume fraction of 45%, CO 2 55% by volume) is fed into a fixed bed reforming reactor 101 at a flow rate of 60L/h (so that the flow rate and the mass space velocity of the methane-containing combustible gas are between 6 and 12L g) -1 h -1 ) The method comprises the steps of carrying out a first treatment on the surface of the The obtained reformed gas enters a fixed bed reactor I201 from a gas conveying pipeline 109 after methane-containing combustible gas is reformed, reacts with an iron-based oxygen carrier, and generates CO after reaction at 850 DEG C 2 And the tail gas of the water vapor through the reduction stage of the oxygen carrierTube 224, in which case fixed bed reactor I enters the oxygen carrier reduction stage. The waste heat recovery unit 301 recovers heat and then pure CO is passed through the gas-liquid separator 2 Into the delivery tube 309.
After the reduction reaction of the oxygen carrier of the fixed bed reactor I201 is finished, valves 208 and 217 are closed through an air inlet end and tail gas end air path control system, valves 207, 216, 211 and 220 are opened, reformed gas is introduced into a fixed bed reactor II202, the fixed bed reactor II enters an oxygen carrier reduction stage, and water vapor from a water vapor inlet header pipe 204 is introduced into the fixed bed reactor I201, wherein the flow rate is 10g/min; CO produced by fixed bed reactor II202 2 And the water vapor enters the oxygen carrier reduction stage waste heat recovery unit 301 through the oxygen carrier reduction stage tail gas conveying pipe 224 for heat recovery, and then passes through the gas-liquid separator for pure CO 2 Entering CO 2 A delivery tube 309; the hydrogen and the water vapor generated by the fixed bed reactor I201 pass through a tail gas conveying pipe 225 in the hydrogen production stage of the water vapor oxidation, the fixed bed reactor I enters a waste heat recovery unit 302 in the hydrogen production stage of the water vapor oxidation for heat recovery, and then the high-purity hydrogen after water removal by condensation enters H 2 A delivery tube 308.
After the reaction of the fixed bed reactor I201 and the fixed bed reactor II202 is finished, valves 207, 216, 211 and 220 are closed, valves 206, 215, 210, 219, 214 and 223 are opened, air enters the fixed bed reactor I201 from an air inlet manifold 205 at a flow rate of 5L/min, water vapor enters the fixed bed reactor II202 from a water vapor inlet manifold 204 at a flow rate of 10g/min, and reformed gas from the fixed bed reforming reactor 101 enters the fixed bed reactor III203 from a methane-containing combustible gas reformed gas conveying pipeline 109. By controlling the gas inlet end gas circuit switching system and the tail gas end gas circuit switching system, the fixed bed reactor III enters an oxygen carrier reduction stage, the fixed bed reactor II enters a steam oxidation hydrogen production stage, and the fixed bed reactor I enters an oxygen carrier air oxidation stage. The tail gas after the oxygen carrier air oxidation reaction in the fixed bed reactor I201 enters the tail gas delivery pipe 226. The air oxidation stage waste heat recovery unit 303 performs heat recovery, and the exhaust gas enters the exhaust gas discharge pipe 307.
The fixed bed reactor I201, the fixed bed reactor II202 and the fixed bed reactor III203 are sequentially and continuously subjected to the oxygen carrier reduction-water vapor oxidation-air oxidation stage, so that the system is ensured to continuously produce high-purity hydrogen (the pressure in the fixed bed reactors I, II and III is maintained at normal pressure to 3 MPa).
The lines 102, 103, 104 may be considered as first intake lines and the lines 111 and 109 may be considered as first exhaust lines in this embodiment. The lines 109, 204, 205 may be considered second intake lines and the lines 224, 225, and 226 may be considered second exhaust lines.
In this embodiment, CO 2 CO collected by the delivery pipe 309 2 Can be used for reforming reaction of methane-containing combustible gas, and can also be directly sealed for CO realization 2 Capturing; the collected condensed water can be used for the hydrogen production reaction by steam oxidation.
In the whole set of the process of the embodiment, the methane-containing combustible gas is used for providing energy. Realize the CO production while preparing high-purity hydrogen 2 And (5) capturing. Reducing the carrier oxygen if used in other ways may result in additional carbon emissions.
In this embodiment, the hydrogen produced is formed from H 2 The delivery tube 308 was vented and the hydrogen output flow was 8L/h for on-line analysis by on-line gas chromatography with the results shown in the following table:
TABLE 1 conditions and results for methane-containing combustible gas reforming coupled with chemical looping to produce high purity hydrogen
Example 2
This example produced hydrogen in the same manner as in example 1, except that hydrogen was produced without subjecting the oxygen carrier to the third-step air oxidation.
Table 2 comparison of technical effects of example 1 and example 2
| Process for producing a solid-state image sensor | Composition of the tail gas of the reduction reactor after cooling | Heat absorption and release conditions of the process |
| Example 1 | 100％CO 2 | Energy self-sustaining |
| Example 2 | 11% CO, H 2 、CH 4 And 89% CO 2 | Requires additional energy |
As can be seen from the comparison of example 1 and example 2, when the oxygen carrier is iron, further oxidation of iron is required to obtain better technical effects; while using, for example, molybdenum, germanium, tungsten as oxygen carrier, no further oxidation of the oxygen carrier is necessary;
only Fe can be produced after the oxidation of water vapor 3 O 4 ，Fe 3 O 4 When the gas reacts with the reformed gas, part of the reformed gas does not participate in the reduction reaction, so that the fuel is wasted and CO is generated 2 ，CO 2 Other impurities are also contained in the mixture, and 100% CO can not be realized 2 And therefore require further oxidation to effect regeneration of the oxygen carrier; in addition, the air oxidation is a strong exothermic reaction, and under certain conditions, the energy generated by the system can provide the required energy for the whole process, so that the effect of energy self-sustaining is achieved.
Comparative example 1
This comparative example 1 is identical to the hydrogen production process of example 1 except that this comparative example does not involve a reforming process to directly feed biogas to the hydrogen production reactor.
TABLE 3 comparison of technical effects of example 1 and comparative example 1
| Purity of hydrogen | Impurity in hydrogen | |
| Example 1 | More than 99 percent | Below the detection line |
| Comparative example 1 | ＜95％ | CO、CO 2 |
Test example:
embodiments of the present application and CO of current large scale hydrogen production technology 2 The emissions were compared as follows:
the prior art comprises the following steps: reforming reaction, high-low temperature shift reaction and PSA (pressure swing adsorption hydrogen production)
1mol CH 4 And 1mol CO 2 The reaction produced 2mol H 2 And 2mol CO (reforming reaction), the generated CO is converted by water gas reaction (high-low temperature conversion reaction), 2mol CO requires 2mol H 2 O (g) gives 2mol of H 2 And 2mol CO 2 The reaction yielded 4mol H in total 2 。
Wherein 1mol of CH 4 And 1mol CO 2 The reaction requires 246.805kJ of energy, 2mol CO and 2H 2 The O (g) reaction gives off 83.3kJ of energy. By alcohol amine absorption method, 1mol CO is absorbed 2 With an energy requirement of 160kJ, then 2mol CO are produced 2 320kJ is required, and the reaction is required altogether246.805+320-82.3= 484.505 kJ; if the energy is derived from CH 4 Combustion to provide (1 molCH 4 803kJ energy provided by combustion), CH 4 Combustion heat efficiency 80%, 484.505/0.8/803=0.75 mol CH 4 Simultaneously produces 0.75mol of CO 2 Thus CO-producing CO 2 The amount of (2) was 0.75mol.
The technical proposal provided by the application
Steam H 2 O production of 4mol H 2 3mol of elemental Fe are required, while 1mol of Fe is produced 3 O 4 And 148.47kJ (steam hydrogen production reaction) is released.
Assuming complete reforming conversion and reformed gases CO and H 2 Reduced iron oxide (Fe 2 O 3 ) Is the same in the amount of CO and H 2 Each need to be reduced to produce 1.5mol of Fe. CO and H 2 Reduction of iron oxide (Fe) 2 O 3 ) Two portions of 1.5mol Fe are produced, 2.25mol CO and 2.25mol H are required 2 CO reduces iron oxide (Fe 2 O 3 ) Releasing 18.75kJ of heat, H 2 Reduction of iron oxide (Fe) 2 O 3 ) 73.2885kJ heat needs to be provided; 2.25mol of CO and 2.25mol of H 2 Requiring reforming of 1.125mol CH 4 And 1.125mol CO 2 And 277.66kJ of heat (oxygen carrier reduction reaction) is required. 1mol Fe 3 O 4 Combustion to form iron oxide (Fe) 2 O 3 ) 118.99kJ of heat is released (oxygen carrier oxidation reaction). The whole process requires 277.66+73.2885-18.75-148.47-118.99 = 64.7385kJ of energy. If the heat is derived from CH 4 Combustion supply (1 molCH) 4 803kJ energy is provided by combustion), the combustion heat efficiency is 80%, 64.7385/0.8/803= 0.100776mol CH is required 4 At the same time release equimolar CO 2 . Then the whole process releases CO 2 The amount of =0.1 mol CO 2 。
That is, the carbon emission of example 1 was 0.55kg CO 2 /kg H 2 The method comprises the steps of carrying out a first treatment on the surface of the The comparative scheme (reforming + high-low temperature shift + PSA) had a carbon emission of 4.125kgCO 2 /kg H 2 . The carbon emission of the preparation is obviously reduced.
From the above results, the present invention provides a composition comprisingThe method for preparing high-purity hydrogen by coupling methane combustible gas reforming with chemical chains has the advantages that the process flow is simple, after the purified biomass fuel gas is reformed by the reforming reactor, the high-purity hydrogen can be obtained in the chemical chain hydrogen production reactor, a complex gas purification device is not needed, the process heat can be self-sustained, and the hydrogen production cost is low; because the solid oxygen carrier is used for transmitting oxygen, CO generated by the reduction of the oxygen carrier can be avoided 2 Is diluted to ensure higher carbon trapping efficiency of the system, so that the hydrogen prepared by the method has the characteristic of low carbon.
Although the embodiments disclosed in the present application are described above, the embodiments are only used for facilitating understanding of the present application, and are not intended to limit the present application. Any person skilled in the art to which this application pertains will be able to make any modifications and variations in form and detail of implementation without departing from the spirit and scope of the disclosure, but the scope of the application is still subject to the scope of the claims appended hereto.
Claims (3)
1. A method for preparing high-purity hydrogen by reforming coupling chemical chains of methane-containing combustible gas, which uses the following devices:
the device comprises: a reforming reactor, a chemical-looping hydrogen production reactor and a controller; the reforming reactor includes a first inlet conduit and a first exhaust conduit configured to communicate the reforming reactor and the chemical looping hydrogen production reactor; the chemical-looping hydrogen production reactor comprises a second air inlet pipeline and a second air outlet pipeline;
the chemical-looping hydrogen production reactor contains an oxygen carrier, and the reforming reactor contains a reforming catalyst; the controller controls the gas entering the chemical-looping hydrogen production reactor;
the controller is used for switching the gas entering the chemical looping hydrogen production reactor to complete three chemical reactions in the chemical looping hydrogen production reactor, wherein the chemical reactions are oxygen carrier reduction reaction, steam hydrogen production reaction and oxygen carrier oxidation reaction, the controller controls the three reactions to be circularly carried out,
the device also comprises a waste heat recovery unit which recovers the heat of the chemical-looping hydrogen production reactor, and the energy generated by the system can provide the required energy for the whole process so as to achieve self-sustaining energy;
the method comprises the following steps:
first, reforming reactions are carried out, i.e. CH in the methane-containing combustible gas 4 And CO 2 Reforming in the reforming reactor to generate reformed gas, and generating H 2 And CO-based synthesis gas;
secondly, carrying out an oxygen carrier reduction reaction, namely reducing the oxygen carrier by the reformed gas, then carrying out a steam hydrogen production reaction, namely, carrying out a hydrogen production reaction by the oxygen carrier in the chemical-looping hydrogen production reactor and steam, and finally carrying out an oxygen carrier oxidation reaction, namely, further oxidizing the oxygen carrier, wherein the oxygen carrier is thoroughly oxidized to be reduced at the moment, so as to complete a cycle;
the oxygen carrier is ferric oxide, and the average particle size of the oxygen carrier is 1mm to 10mm;
the air inlet end of the reforming reactor is connected with nitrogen or air or steam or CO 2 A delivery pipe for delivering the nitrogen, air, steam or CO 2 Nitrogen or air or water vapour or CO on the conveying pipe 2 The inlet control valve controls the gas delivery to be closed;
CH in the methane-containing combustible gas provided to the reforming reactor 4 Volume fraction of 45%, CO 2 Is 55% by volume;
the flow mass airspeed of the methane-containing combustible gas is 6L g -1 h -1 To 12L g -1 h -1 。
2. The method of claim 1, wherein,
the reaction temperatures of the oxygen carrier reduction reaction, the steam hydrogen production reaction and the oxygen carrier oxidation reaction are 570-1000 ℃;
the reaction pressure of the oxygen carrier reduction reaction, the steam hydrogen production reaction and the oxygen carrier oxidation reaction is normal pressure to 3MPa.
3. The method of claim 1, wherein,
the reaction temperature of the reforming reaction is 500-1000 ℃;
the reaction pressure of the reforming reaction is normal pressure;
the methane-containing combustible gas comprises any one or more of biogas, biomass pyrolysis gas, coal-based synthesis gas and natural gas.
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