CN113753857A - Process for preparing high-purity hydrogen by methane-containing combustible gas reforming coupling chemical chain and application - Google Patents
Process for preparing high-purity hydrogen by methane-containing combustible gas reforming coupling chemical chain and application Download PDFInfo
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- 239000000126 substance Substances 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
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- 238000006057 reforming reaction Methods 0.000 claims description 11
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
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- 239000002028 Biomass Substances 0.000 claims description 7
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- 229910052593 corundum Inorganic materials 0.000 claims description 7
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- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
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- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 description 33
- 238000011084 recovery Methods 0.000 description 22
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- 239000000446 fuel Substances 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910002845 Pt–Ni Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- -1 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 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
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Images
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (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 methane-containing combustible gas reforming coupling chemical chains and application thereof, wherein the process comprises a reforming reactor, a hydrogen production reactor and a controller; the reforming reactor comprises a first gas inlet line and a first gas outlet line, the first gas outlet line being configured to communicate the reforming reactor with 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 gas entering the hydrogen production reactor so as to complete two chemical reactions 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 the advantages of high hydrogen purity, low carbon, simple operation,
High efficiency and the like.
Description
Technical Field
The invention relates to but is not limited to the field of clean energy and the field of thermochemical hydrogen production, in particular to but not limited to a methane-containing combustible gas hydrogen production process and application.
Background
As a chemical raw material and an energy carrier, compared with other fuels, hydrogen does not produce CO when being used2And the like, and thus hydrogen energy is an important medium for achieving global "carbon neutralization" goals in the future. However, hydrogen is usually present in the environment in the form of compounds such as H2O or CnHmThe preparation of elemental hydrogen requires a relatively large input of energy. In addition, the hydrogen fuel cell is taken as an important hydrogen using unit, the requirement on the purity of hydrogen is usually more than or equal to 99.9 percent, and therefore, the technology for efficiently preparing high-purity hydrogen becomes a crucial step for realizing large-scale popularization and application of hydrogen energy.
The mature process route in the prior hydrogen production technology is a combined process of natural gas steam reforming, and then water gas conversion and pressure swing adsorption separation. However, the energy structure of 'rich coal, oil and gas lack' in China is not suitable for developing natural gas hydrogen production. On the contrary, China has abundant coal-based synthesis gas and biomass fuel gas, and the gas can be used for preparing hydrogen. Coal-based synthesis gas and biomass fuel gas are used as mixed gas, and CH is usually used as the mixed gas4、CO2、H2And mainly CO. Although these gases may be converted to H by steam reforming2And CO, and then converted into H by water gas2And CO2And finally, purifying and decarbonizing the obtained gas to prepare high-purity hydrogen. However, due to the long technical route, gas purification process and CO2The 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 present 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 reforming methane-containing combustible gas and coupling a chemical chain and a methane-containing combustible gas reforming catalyst, on one hand, high-purity hydrogen can be prepared, and on the other hand, low-cost CO can be realized2Trapping and heat energy recovery.
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 comprises a first gas inlet line and a first gas outlet line, the first gas outlet line being configured to communicate the reforming reactor with 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 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 the like, or, alternatively,
the controller is used for switching gas entering the hydrogen production reactor, so that three chemical reactions are completed in the hydrogen production reactor, wherein the chemical reactions comprise an oxygen carrier reduction reaction, a steam hydrogen production reaction and an oxygen carrier oxidation reaction, and the controller controls two reaction cycles to be carried out.
The method comprises the steps of utilizing a catalyst in a reforming reactor and converting the catalyst, taking combustible gas based on biomass as a raw material of the reforming reactor, and reducing an oxygen carrier in a reduction reactor of a chemical-looping hydrogen production reactor by the prepared reformed gas. CO production of CO by oxidation of reformed gas2And water, to CO after simple cooling at the gas outlet2And carrying out trapping, sealing and utilization.
In one embodiment provided by the present application, when the hydrogen production reactor performs an oxygen carrier reduction reaction, the controller controls the gas entering the hydrogen production reactor to be the gas produced by the reforming reactor;
when the hydrogen production reactor performs a hydrogen production reaction by using steam, the controller controls the gas entering the hydrogen production reactor to be the steam;
when the hydrogen production reactor carries out oxygen carrier oxidation reaction, the controller controls the gas entering the hydrogen production reactor to be air or oxygen.
In one embodiment provided herein, the number of the hydrogen production reactors is two or more, and the number of the hydrogen production reactors is not less than the number of the chemical reactions to be performed in the hydrogen production reactors.
In one embodiment provided herein, the controller is configured to switch the gas entering different hydrogen production reactors such that different reactions occur simultaneously, the hydrogen production reactors being capable of producing hydrogen without interruption.
In one embodiment provided by the present application, the apparatus for preparing high purity hydrogen further comprises a gas inlet end gas circuit switching system and a gas outlet end gas circuit switching system;
the controller controls the air inlet end air path switching system and the tail gas end air path switching system; the gas path switching system at the gas inlet end is communicated with the hydrogen production reactor and is configured to introduce gas into the hydrogen production reactor;
the tail gas end gas path 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 moment, the hydrogen production reactor is respectively in different reaction stages under the control of the controller, the gas inlet end gas circuit switching system and the tail gas end gas circuit switching system;
and at different moments, the same fixed bed reactor is in different reaction states under the control of the controller, the gas inlet end gas circuit switching system and the tail gas end gas circuit switching system.
In one embodiment provided herein, the apparatus may further include a waste heat recovery unit; optionally, the pre-heated 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 in the first charge may be a fully oxidised oxide of one or more of molybdenum, germanium, tungsten, iron. The metal element can be the above metal element, and the reformed gas is used for reducing oxides possibly existing in the metal element.
In one embodiment provided herein, the average particle size of the oxygen carrier is 1mm to 10 mm.
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 is subjected to an oxygen gain-oxygen loss cycle.
In one embodiment provided herein, the reforming catalyst is selected from the group consisting of Ni/MgO, Ni/Al2O3、Ni/CeO2、Ni/TiO2、Ni/Fe2O3、Ni/SiO2、Pt/MgO、Pt/Al2O3、Pt/CeO2、Pt/TiO2、Pt/Fe2O3、Pt/SiO2、NiPt/MgO、NiPt/Al2O3、NiPt/CeO2、NiPt/TiO2、NiPt/Fe2O3And NiPt/SiO2Any one or more of;
in one embodiment, the MgO and Al are mixed2O3、CeO2、TiO2、Fe2O3、SiO2The catalyst is a carrier, the Ni element and the Pt element are active components, the active components are attached to the carrier, the Pt element in the active components accounts for 1-3% of the weight of the carrier, and the Ni element in the active components accounts for 5-20% of the weight of the carrier according to the weight content of the final reforming catalyst.
In one embodiment provided herein, the reforming catalyst has an average particle size of 0.45mm to 2 mm.
In one embodiment provided herein, the inlet end (gas furnace system) of the reforming reactor may be fed with methane-containing combustible gas, and the reforming reactor atmosphere may be adjusted as needed, for example, with H2Water vapor, CO2Or O2For activating or regenerating the catalyst for the reforming reaction, for improving the efficiency of the reforming reactor and for adjusting the gas ratio in the reforming reactor.
In one embodiment provided herein, the inlet end (gas furnace system) of the reforming reactor may be fed with methane-containing combustible gas, and the reforming reactor atmosphere may be adjusted as needed, for example, with H2Water vapor, CO2Or O2For activating or regenerating the catalyst for the reforming reaction, for improving the efficiency of the reforming reactor and for adjusting the gas ratio in the reforming reactor.
In another aspect, the present application provides a chemical looping hydrogen production process, which uses the above-mentioned apparatus, and comprises the following steps:
first, a methane-containing combustible gas and CO2Reforming to generate reformed gas;
secondly, the reforming gas reduces the oxygen carrier, then the oxygen carrier reacts with water vapor to produce hydrogen, and at the moment, the oxygen carrier is thoroughly oxidized to be reduced, so that one cycle is completed;
or the like, or, alternatively,
secondly, the reforming gas reduces the oxygen carrier, then the oxygen carrier reacts with water vapor to produce hydrogen, and finally the oxygen carrier is further oxidized, and the oxygen carrier is thoroughly oxidized to be reduced, so that one cycle is completed;
in one embodiment provided herein, the CO is generated after the CO reacts with the oxygen carrier2Participating in reforming of the methane-containing combustible gas, the H2H generated after reaction with oxygen carrier2Reacting O with the oxygen carrier and water vapor 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 performed in different reactors, respectively.
In one embodiment provided herein, the reaction temperature of the oxygen carrier reduction reaction, the steam 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 steam hydrogen production reaction, and the oxygen carrier oxidation reaction is from normal pressure to 3 MPa.
For the hydrogen production reactor, the steam flow and air flow do not need to be specially calibrated, since both reactions are not kinetically controlled.
In one embodiment provided herein, the reaction temperature of the reforming reaction is from 500 ℃ to 1000 ℃;
in one embodiment provided herein, the reaction pressure of the reforming reaction is atmospheric pressure;
in one embodiment provided herein, the methane-containing combustible gas has a flow mass space velocity of 6L g-1h-1To 12L g-1h-1；
In one embodiment provided herein, the methane-containing combustible gas comprises any one or more of biogas, biomass pyrolysis gas, coal-based synthesis gas, and natural gas;
in one embodiment provided herein, the methane-containing combustible gas comprises CO2A volume fraction of 10 vol.% to 80 vol.%, a volume fraction of methane of 20% to 70%;
in one embodiment provided herein, the balance gas comprises H2、CO、C2H4And C2H6Preferably, C is2H4And C2H6Less than 5 vol.% of one or both. 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 application provides a device and a method for preparing high-purity green hydrogen by biomass gas reforming coupling chemical chain, which achieve the following technical effects:
1. the methane-containing combustible gas directly enters a reforming reactor, and CH is converted by using a reforming catalyst4And CO2Converted into synthesis gas in a reforming reactor CH4And CO2The conversion rates respectively reach more than 95 percent and 90 percent. Meanwhile, the problem of reduction of hydrogen purity caused by carbon deposition of the oxygen carrier is avoided.
2. The reformed fuel gas is mainly synthesis gas (H)2And CO) is mainly used, the reaction rate of the CO 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 H-containing gas produced in the chemical-looping hydrogen production reactor is mainly used2The product is subjected to simple condensation and dehydration to obtain high-purity H2(the purity is more than or equal to 99 percent), does not need a complex gas purification device, and has simple operation and low hydrogen production cost. 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-Fe2O3)。
3. The stages of oxygen carrier reduction, steam hydrogen production and oxygen carrier oxidation are spatially separated, so that CO generated in the stage of oxygen carrier reduction can be avoided2(the purity is more than or equal to 99 percent) is diluted, so that the system has high carbon capture efficiency;
4. the application is in the utilization of CH4、H2At the same time as CO, part of the CO is removed2Convert into CO for utilization and simultaneously carry out CO2The high-purity hydrogen prepared by the method has the characteristic of low carbon;
5. when the chemical-looping hydrogen production reactor obtains the target product, 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 the practice of the application. Other advantages of the present application may be realized and attained by the invention in its aspects as described in the specification.
Drawings
The accompanying drawings are included to provide an understanding of the present disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the examples serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a schematic diagram of a device for preparing high-purity hydrogen by reforming methane-containing combustible gas and coupling a chemical chain.
In fig. 1, the reference numerals are as follows: a-a methane-containing combustible gas reforming reactor; b-chemical chain hydrogen production reactor; c, a waste heat recovery unit; 101-fixed bed reforming reactor; 102-a methane-containing gas conveying pipeline; 103-nitrogen or air or water vapor or CO2A delivery pipe; 104-hydrogen conveying pipe; 105-inlet control valve of methane-containing combustible gas; 106-nitrogen or air or steam or CO2An inlet control valve; 107-hydrogen inlet control valve; 108-a tail gas control valve after methane-containing combustible gas reforming; 109-a gas conveying pipeline for reformed methane-containing combustible gas; 110-fixed bed reforming reactor tail gas control valve; 111-fixed bed reforming reactor off-gas discharge pipe;
201-fixed bed reactor I; 202-fixed bed reactor II; 203-fixed bed reactor III; 204-water vapor inlet manifold; 205-air inlet manifold; 206-fixed bed reactor I air inlet control valve; 207-steam inlet control valve of fixed bed reactor I; 208-fixed bed reactor I reformed gas inlet control valve; 209-fixed bed reactor II air inlet control valve; 210-fixed bed reactor II steam inlet control valve; 211-fixed bed reactor II reformed gas inlet control valve; 212-fixed bed reactor III air inlet control valve; 213-steam inlet control valve of fixed bed reactor III; 214-fixed bed reactor III reformed gas inlet control valve;
215-fixed bed reactor I air oxidation stage tail gas control valve; 216-fixed bed reactor I steam oxidation hydrogen production stage tail gas control valve; 217-fixed bed reactor I tail gas control valve after oxygen carrier reduction; 218-a tail gas control valve of an air oxidation stage of the fixed bed reactor II; 219-fixed bed reactor II steam oxidation hydrogen production stage tail gas control valve; 220-a tail gas control valve after reduction of an oxygen carrier of the fixed bed reactor II; 221-fixed bed reactor III air oxidation stage tail gas control valve; 222-a tail gas control valve of a steam oxidation hydrogen production stage of the fixed bed reactor III; 223-tail gas control valve after oxygen carrier reduction of the fixed bed reactor III; 224-tail gas conveying pipe of oxygen carrier reduction stage; 225-tail gas delivery pipe in hydrogen production stage by steam oxidation; 226-air oxidation stage tail gas transfer pipe;
301-waste heat recovery unit in oxygen carrier reduction stage; 302-a waste heat recovery unit in the hydrogen production stage by steam oxidation; 303-an oxygen carrier air oxidation stage waste heat recovery unit; 304-boiler water inlet manifold; 305-a circulating cooling water inlet manifold; 306-condensate outlet manifold; 307-tail gas discharge pipe; 308-H2A delivery pipe; 309-CO2A delivery pipe; 310-a waste heat recovery device steam main; 311-circulating cooling water outlet manifold.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application are described in detail below. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The present invention will be described in further detail below with reference to the accompanying drawings, but the present invention is not limited thereto.
As shown in fig. 1, in a preferred embodiment of the present invention, an apparatus for preparing high-purity hydrogen by reforming methane-containing combustible gas coupled with a chemical looping comprises a methane-containing combustible gas reforming reactor a, a chemical looping hydrogen production reactor B, and a waste heat recovery unit C;
the specific process comprises the following steps:
step 1: firstly, opening valves 106 and 110, keeping the other valves closed, introducing nitrogen or other inert atmosphere gas through a pipeline 103, heating the fixed bed reforming reactor 101 to a proper temperature of 500-1000 ℃ under the inert atmosphere, maintaining the temperature, closing the valve 106 after the temperature is constant, opening the valve 107, introducing hydrogen, activating the catalyst, closing the valve 107 after the activation is finished, and continuously introducing nitrogen for purging. At the same time, the fixed-bed reactors I, II, III start to warm up to a constant temperature of 570 ℃ to 1000 ℃ and maintain this temperature.
Step 2: 2.1) opening the valves 105, 108, 208 and 217, closing all the other valves, introducing the methane-containing combustible gas into the fixed bed reforming reactor 101 through a pipeline 102, conveying the gas reformed by the fixed bed reforming reactor 101 into the fixed bed reactor I201 through a pipeline 109 for oxygen carrier reduction reaction (at the moment, oxygen in the oxygen carrier participates in the reaction, and collecting pure CO through condensation of generated water vapor to generate tail gas2) (ii) a After the reduction reaction of the oxygen carrier is finished (i.e. when the reformed gas starts to penetrate the bed), the valves 208 and 217 are closed;
2.2) opening valves 207, 216, 211 and 220, and then carrying out a hydrogen production reaction by steam oxidation in the fixed bed reactor I201 (high-purity hydrogen can be collected by condensation of reaction tail gas), and simultaneously carrying out an oxygen carrier reduction reaction in the fixed bed reactor II 202; when the steam oxidation hydrogen production reaction in 201 and the oxygen carrier reduction reaction in 202 are finished, the valves 207, 216, 211 and 220 are closed;
2.3) opening valves 206, 215, 210, 219, 214 and 223, and closing valves 206, 215, 210, 219, 214 and 223 when the air oxidation reaction in the fixed bed reactor I201, the steam oxidation hydrogen production reaction in the fixed bed reactor II202 and the oxygen carrier reduction reaction in the fixed bed reactor III203 are finished;
2.4) opening the valves 208, 217, 209, 218, 213 and 222, leading the fixed bed reactor I201 to enter the next cycle to start oxygen carrier reduction reaction, leading the fixed bed reactor II202 to generate air oxidation reaction, leading the fixed bed reactor III203 to generate hydrogen through steam oxidation, and closing the valves 208, 217, 209, 218, 213 and 222 when the reaction is finished.
2.5) opening the valves 207, 216, 211 and 220, 212 and 221, starting the next cycle of hydrogen production reaction by steam oxidation in the fixed bed reactor I201, wherein the oxygen carrier reduction reaction occurs in the fixed bed reactor II202, the air oxidation reaction occurs in the fixed bed reactor III203, and closing the valves 207, 216, 211 and 220, 212 and 221 when the reaction is finished.
By repeating the step 2, the fixed bed reactors 201, 202 and 203 are controlled to be in any one of oxygen carrier reduction reaction, steam oxidation hydrogen production reaction and oxygen carrier air oxidation reaction respectively through the air inlet end air path control system and the tail gas short air path switching system at the same time, and the continuous hydrogen production can be ensured by unifying different reactions carried out by different reactors at the same time.
And 2, recovering the waste heat by the waste heat recovery unit 301 in the oxygen carrier reduction stage, the waste heat recovery unit 302 in the hydrogen production stage by steam oxidation and the waste heat recovery unit 303 in the oxygen carrier air oxidation stage.
The methane-containing combustible gas can realize continuous high-purity hydrogen preparation through the reforming reactor and the chemical-looping hydrogen production reactor, reduces the complicated purification process in the traditional hydrogen production process, and simultaneously realizes CO2Trapping and waste heat recovery, and improving the energy efficiency of the system.
Example one
The embodiment provides a method for preparing high-purity hydrogen by reforming methane-containing combustible gas and coupling a chemical chain and a reforming catalyst for methane-containing combustible gas, as shown in fig. 1, firstly reforming methane-containing combustible gas in a fixed bed reforming reactor, and then preparing high-purity hydrogen by using the reformed gas as a fuel of a chemical chain hydrogen production reactor, wherein the specific method comprises the following steps:
the preparation of the reforming catalyst in the invention is specifically as follows: the water absorption of the commercial MgO powder was first measured to be 4.72mL/g MgO. According to the Pt: 1% of (Pt + Ni + MgO), and Ni: weighing corresponding nickel nitrate hexahydrate and chloroplatinic acid according to the mass percent of (Pt + Ni + MgO) of 10%, preparing a solution with corresponding deionized water, mixing the salt solution and 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, and 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 (iron sesquioxide, 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.
The Pt-Ni of the inventionFilling MgO catalyst 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 ℃ under the condition that the other 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 1 h; closing the valve 107, opening the valve 106 to purge for 30min, simultaneously heating the fixed bed reactor I201, the fixed bed reactor II202 and the fixed bed reactor III203 to 850 ℃, opening the valves 105, 108, 208 and 217 after the temperature is constant, closing all the other valves, and pumping the biogas (CH in the biogas) by a pipeline 1024Volume fraction of 45%, CO255 percent by volume) is fed into the fixed bed reforming reactor 101 at a flow rate of 60L/h (so that the flow mass space velocity of the methane-containing combustible gas is 6-12L g-1h-1) (ii) a The prepared reformed gas enters a fixed bed reactor I201 from a gas conveying pipeline 109 after the methane-containing combustible gas is reformed, and reacts with an iron-based oxygen carrier at 850 ℃ to generate CO2And the water vapor passes through the tail gas delivery pipe 224 of the oxygen carrier reduction stage, at which time the 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 a gas-liquid separator2Into duct 309.
After the oxygen carrier reduction reaction of the fixed bed reactor I201 is finished, closing the valves 208 and 217 through the gas path control system at the gas inlet end and the tail gas end, opening the valves 207, 216, 211 and 220, introducing reformed gas into the fixed bed reactor II202, introducing the water vapor from the water vapor inlet header pipe 204 into the fixed bed reactor I201 at the oxygen carrier reduction stage, wherein the flow rate is 10 g/min; CO production by fixed bed reactor II2022And the water vapor enters the waste heat recovery unit 301 of the oxygen carrier reduction stage through the tail gas conveying pipe 224 of the oxygen carrier reduction stage for heat recovery, and then pure CO is separated by the gas-liquid separator2Into CO2Delivery pipe 309; hydrogen and steam generated by the fixed bed reactor I201 pass through a tail gas conveying pipe 225 in a hydrogen production stage of steam oxidation, the fixed bed reactor I enters a waste heat recovery unit 302 in the hydrogen production stage of steam oxidation for heat recovery, and high-purity hydrogen obtained after water removal through condensation enters H2 A delivery pipe 308.
After the reaction of the fixed bed reactor I201 and the fixed bed reactor II202 is finished, the valves 207, 216, 211 and 220 are closed, the valves 206, 215, 210, 219, 214 and 223 are opened, air enters the fixed bed reactor I201 from the air inlet manifold 205 at the flow rate of 5L/min, water vapor enters the fixed bed reactor II202 from the water vapor inlet manifold 204 at the flow rate of 10g/min, and reformed gas from the fixed bed reforming reactor 101 enters the fixed bed reactor III203 from the reformed gas conveying pipeline 109 of the methane-containing combustible gas. And (3) under the control of 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 oxidation reaction of the oxygen carrier air in the fixed bed reactor I201 enters a tail gas conveying pipe 226. The waste heat recovery unit 303 in the air oxidation stage performs heat recovery, and the tail gas enters a tail gas discharge pipe 307.
The fixed bed reactor I201, the fixed bed reactor II202 and the fixed bed reactor III203 sequentially and continuously go through the stages of oxygen carrier reduction, steam oxidation and air oxidation, and high-purity hydrogen is ensured to be continuously produced by the system (the pressure in the fixed bed reactors I, II and III is maintained to be between normal pressure and 3 MPa).
The lines 102, 103, 104 in this embodiment may be considered as first intake lines, and the line 111 and the line 109 may be considered as first exhaust lines. The lines 109, 204, 205 may be considered second inlet lines, and the lines 224, 225 and 226 may be considered second outlet lines.
In this example, CO2CO collected by duct 3092Can be used for reforming reaction of combustible gas containing methane, and can also be directly sealed for realizing CO2Trapping; the collected condensed water can be used for the hydrogen production reaction by steam oxidation.
In this example, a methane-containing combustible gas was used to provide energy for the overall process. Realizes the CO production while preparing the high-purity hydrogen2And (4) trapping. Additional carbon emissions may result if the oxygen carrier is reduced by other means.
This implementationIn the example, the hydrogen produced is derived from H2The hydrogen flows out of the delivery pipe 308, the output flow rate of the hydrogen is 8L/h, and the on-line analysis is carried out by an on-line gas chromatograph, and the results are shown in the following table:
TABLE 1 conditions and results for reforming methane-containing combustible gas coupled with chemical looping to produce high purity hydrogen
Example 2
This example produced hydrogen in the same process as example 1, except that hydrogen was produced without passing through the third step of air oxidation oxygen carrier.
Table 2 comparison of the technical effects of example 1 and example 2
| Process for the preparation of a coating | Composition of reduction reactor tail gas after cooling | Heat absorption and release conditions of the process |
| Example 1 | 100％CO2 | Energy self-sustaining |
| Example 2 | 11% of CO and H2、CH4And 89% CO2 | Need to provide 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 effect; when molybdenum, germanium and tungsten are used as oxygen carriers, further oxidation operation of the oxygen carriers is not needed;
only Fe can be generated after steam oxidation3O4，Fe3O4When the reformed gas reacts with the reformed gas, part of the reformed gas does not participate in the reduction reaction, resulting in the waste of fuel and the generation of CO2，CO2The product also contains other impurities, and can not realize 100% CO2So further oxidation is required to effect regeneration of the oxygen carrier; in addition, air oxidation is a strong exothermic reaction, and under a certain condition, energy generated by the system can provide required energy for the whole process, so that the effect of self-sustaining energy is achieved.
Comparative example 1
Comparative example 1 is the same as the hydrogen production process of example 1 except that the comparative example does not involve a reforming process to directly pass biogas to the hydrogen production reactor.
Table 3 comparison of technical effects of example 1 and comparative example 1
| Purity of hydrogen | Impurities in hydrogen | |
| Example 1 | Greater than 99% | Below the detection line |
| Comparative example 1 | ＜95％ | CO、CO2 |
Test example:
CO of embodiments of the present application and current large scale hydrogen production technologies2The emissions comparisons were as follows:
the prior art is as follows: reforming reaction + high-low temperature conversion reaction + PSA (pressure swing adsorption hydrogen production)
1mol CH4And 1mol of CO2Reaction to give 2mol of H2And 2mol CO (reforming reaction), the CO produced being shifted by the water gas reaction (high-low temperature shift reaction), 2mol H being required for 2mol CO2O (g) 2mol of H2And 2molCO2The reaction gives 4mol of H2。
Wherein 1mol of CH4And 1mol of CO2The reaction requires 246.805kJ of energy, 2mol of CO and 2H2O (g) the reaction gave 83.3kJ of energy. Absorbing 1mol of CO by utilizing an alcohol amine absorption method2Requiring 160kJ of energy, 2mol of CO are produced2The reaction needs 320kJ, and the total energy of 246.805+320-82.3 is 484.505 kJ; if the energy is derived from CH4Combustion to provide (1 molCH)4Combustion providing 803kJ of energy), CH4The combustion thermal efficiency was 80%, then 484.505/0.8/803 became 0.75mol of CH4While generating 0.75mol of CO2Thus, CO-production of CO2The amount of (B) was 0.75 mol.
The technical scheme provided by the application
Steam H2Production of 4mol H from O23mol of Fe simple substance is needed, and 1mol of Fe is generated simultaneously3O4And 148.47kJ is released (water vapor hydrogen production reaction).
Assuming complete conversion of the reforming, and reforming gases CO and H2Reduced iron oxide (Fe)2O3) In the same amount, CO and H2Each of these was reduced to yield 1.5mol of Fe. CO and H2Separately reducing iron oxide (Fe)2O3) Two 1.5mol Fe were produced, 2.25mol CO and 2.25mol H2CO reduction of iron oxide (Fe)2O3) Release 18.75kJ of heat, H2Reduced iron oxide (Fe)2O3) Need to provide 73.2885kJ heat; 2.25mol of CO and 2.25mol of H2It is necessary to reform 1.125mol of CH4And 1.125mol of CO2And requires 277.66kJ of heat (oxygen carrier reduction reaction). 1mol of Fe3O4Combustion to iron oxide (Fe)2O3) Releasing 118.99kJ of heat (oxygen carrier oxidation reaction). The whole process requires energy of 277.66+ 73.2885-18.75-148.47-118.99-64.7385 kJ. If the heat is derived from CH4Combustion supply (1 molCH)4803kJ energy is provided by combustion), the thermal efficiency of combustion is 80%, 64.7385/0.8/803 is required to be 0.100776mol CH4While releasing equimolar CO2. Then the whole process releases CO2The amount of (C) is 0.1mol of CO2。
That is, the carbon emission of example 1 was 0.55kgCO2/kg H2(ii) a The carbon emission for the comparative scheme (reforming + high and low temperature conversion + PSA) was 4.125kgCO2/kg H2. The emission of the prepared carbon is obviously reduced.
According to the results, the method for preparing high-purity hydrogen by reforming the methane-containing combustible gas and coupling the chemical chain is simple in process flow, the purified biomass fuel gas can be 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; as the solid oxygen carrier is used for transmitting oxygen, CO generated by reduction of the oxygen carrier can be avoided2Is diluted to ensure the higher carbon capture efficiency of the system, so the hydrogen prepared by the method has the characteristic of low carbon.
Although the embodiments disclosed in the present application are described above, the descriptions are only for the convenience of understanding the present application, and are not intended to limit the present application. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the appended claims.
Claims (10)
1. An apparatus for preparing high-purity hydrogen comprises a reforming reactor, a hydrogen production reactor and a controller; the reforming reactor comprises a first gas inlet line and a first gas outlet line, the first gas outlet line being configured to communicate the reforming reactor with 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 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 the like, or, alternatively,
the controller is used for switching gas entering the hydrogen production reactor, so that three chemical reactions are completed in the hydrogen production reactor, wherein the chemical reactions comprise oxygen carrier reduction reaction, steam hydrogen production reaction and oxygen carrier oxidation reaction, and the controller controls the three reactions to be carried out circularly.
2. The apparatus of claim 1, wherein 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 a hydrogen production reaction by using steam, the controller controls the gas entering the hydrogen production reactor to be the steam;
when the hydrogen production reactor carries out oxygen carrier oxidation reaction, the controller controls the gas entering the hydrogen production reactor to be air or oxygen.
3. The apparatus of claim 2 wherein there are more than two hydrogen production reactors and the number of hydrogen production reactors is no less than the number of chemical reactions to be performed in the hydrogen production reactors.
4. The apparatus of claim 3 wherein the controller is configured to switch the gas entering different hydrogen production reactors such that different reactions occur simultaneously, the hydrogen production reactors being capable of producing hydrogen without interruption.
5. The apparatus of claim 3 or 4, wherein the apparatus for producing high purity hydrogen further comprises a gas inlet end gas circuit switching system and a gas outlet end gas circuit switching system;
the controller controls the air inlet end air path switching system and the tail gas end air path switching system; the gas path switching system at the gas inlet end is communicated with the hydrogen production reactor and is configured to introduce gas into the hydrogen production reactor;
the tail gas end gas path 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 moment, the hydrogen production reactor is respectively in different reaction stages under the control of the controller, the gas inlet end gas circuit switching system and the tail gas end gas circuit switching system;
and at different moments, the same fixed bed reactor is in different reaction states under the control of the controller, the gas inlet end gas circuit switching system and the tail gas end gas circuit switching system.
6. The apparatus of any one of claims 1 to 4, wherein the oxygen carrier comprises one or more of molybdenum, germanium, tungsten, and iron;
optionally, the average particle size of the oxygen carrier is 1mm to 10 mm.
7. The apparatus of any one of claims 1 to 4, wherein the reforming reactor contains a reforming catalyst;
optionally, the reforming catalyst is selected from Ni/MgO, Ni/Al2O3、Ni/CeO2、Ni/TiO2、Ni/Fe2O3、Ni/SiO2、Pt/MgO、Pt/Al2O3、Pt/CeO2、Pt/TiO2、Pt/Fe2O3、Pt/SiO2、NiPt/MgO、NiPt/Al2O3、NiPt/CeO2、NiPt/TiO2、NiPt/Fe2O3And NiPt/SiO2Any one or more of;
alternatively, the MgO and Al2O3、CeO2、TiO2、Fe2O3、SiO2The catalyst is a carrier, the Ni element and the Pt element are active components, the active components are attached to the carrier, and the Pt element in the active components accounts for 1-3% of the weight of the carrier, and the Ni element in the active components accounts for 5-20% of the weight of the carrier according to the weight content of the final reforming catalyst;
optionally, the reforming catalyst has an average particle size of 0.45mm to 2 mm.
8. A chemical looping hydrogen production process using the apparatus of any one of claims 1 to 7, comprising the steps of:
first, a methane-containing combustible gas and CO2Reforming to generate reformed gas;
secondly, the reforming gas reduces the oxygen carrier, then the oxygen carrier reacts with water vapor to produce hydrogen, and at the moment, the oxygen carrier is thoroughly oxidized to be reduced, so that one cycle is completed;
or the like, or, alternatively,
secondly, the reforming gas reduces the oxygen carrier, then the oxygen carrier reacts with water vapor to produce hydrogen, and finally the oxygen carrier is further oxidized, and the oxygen carrier is thoroughly oxidized to be reduced, so that one cycle is completed;
optionally, the CO is generated after the CO reacts with the oxygen carrier2Participating in reforming of the methane-containing combustible gas, the H2H generated after reaction with oxygen carrier2Reacting O with the oxygen carrier and water vapor to produce hydrogen;
optionally, the reforming reaction, the oxygen carrier reduction reaction, the steam hydrogen production reaction, and the oxygen carrier oxidation reaction are respectively performed in different reactors.
9. The method of claim 8, wherein 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 ℃;
optionally, the reaction pressure of the oxygen carrier reduction reaction, the steam hydrogen production reaction and the oxygen carrier oxidation reaction is normal pressure to 3 MPa.
10. The process of claim 8 or 9, wherein the reaction temperature of the reforming reaction is 500 ℃ to 1000 ℃;
optionally, the reaction pressure of the reforming reaction is atmospheric pressure;
optionally, the flow mass space velocity of the methane-containing combustible gas is 6L g-1h-1To 12L g-1h-1；
Optionally, the methane-containing combustible gas comprises any one or more of biogas, biomass pyrolysis gas, coal-based synthesis gas and natural gas;
optionally, CO in the methane-containing combustible gas2A volume fraction of 10 vol.% to 80 vol.%, a volume fraction of methane of 20% to 70%;
optionally, the balance gas comprises H2、CO、C2H4And C2H6Preferably, C is2H4And C2H6Less than 5 vol.% of one or both.
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